Olefin polymerization catalyst system useful for polar monomers

ABSTRACT

This invention relates to a polymerization method comprising contacting at least one olefin monomer, at least one polar monomer, an optional activator, and a catalyst compound represented by the formula:  
                 
 
     wherein M is selected from groups 3-11 of the periodic table;  
                 
 
     L 1  represents a formal anionic ligand, L 2  represents a formal neutral ligand, a is an integer greater than or equal to 1; b is greater than or equal to 0; c is greater than or equal to 1,  
     E is nitrogen or phosphorus, Ar 0  is arene, R 1 -R 4  are, each independently, selected from hydrogen, hydrocarbyl, substituted hydrocarbyl or functional group, provided however that R 3  and R 4  do not form a naphthyl ring, N is nitrogen and O is oxygen.

CROSS REFERENCE TO RELATED APPLICATION

[0001] The present application is a Continuation-in-Part of U.S.application Ser. No. 10/436,741, filed May 13, 2003.

FIELD OF THE INVENTION

[0002] This invention relates to novel processes to polymerize oroligomerize olefin monomers with polar monomers using novelphenoxide-containing transition metal compounds and polymers producedtherefrom.

BACKGROUND OF THE INVENTION

[0003] The present invention is directed toward new transition metalcompounds containing bidentate E-phenoxide ligands and formal neutralligands that are useful for the oligomerization and polymerization ofolefins. Bidentate E-phenoxide ligands form 6-membered metallacyclerings when bound to a transition metal. These compounds, and optionallyan activator, can be used to oligomerize or polymerize unsaturatedmonomers such as olefins.

[0004] Other polymerization catalysts employing bidentate ligands basedon phenoxides that form six-membered metallacycle rings have beenreported in the art. Mitsui has reported low activity transition metalcomplexes containing azo-phenoxide ligands (European Patent EP-A1 0 990664). Low activity, low molecular weight catalysts that use anazo-phenoxide ligand based upon a naphthyl ring have also been reportedin the literature (Macromolecules, 2002, 35, 6071). Catalysts based uponketo-amide structures have been reported by DuPont (WO 98/30609). Theseshow poor activity and low molecular weight or poor molecular weightcontrol. Imine-phenoxide catalysts based on nickel have been reportedboth by Grubbs (Science 2000, 287, 460; Organometallics 1998, 17, 3149;J. Polym. Sci. A. 2002, 40, 2842; WO 98/42665; WO 2000/56786; WO2000/56787; WO 2000/56781) and DuPont researchers (WO 98/30609). Theseimine-phenoxide systems were examined alongside the azo-phenoxidecatalysts reported here and the imine-phenoxide systems were shown togive lower molecular weight polymer.

[0005] Other references of interest include: WO 98/42664; Hicks, F.;Brookhart, M. Organometallics 2001, 20, 3217; Laali, K.; Szele, I.;Zollinger, H., Helvetica Chimica Acta 1983, 66, 1737; and Petrillo, G.;Novi, M.; Garbarino, G.; Filiberti, M., Tetrahedron 1989, 45, 7411.

[0006] Functionalized polyolefins are of interest for many industrialapplications due to the polymer property enhancements bestowed by polargroups. These advantages can include improved impact strength, adhesion,dyeability, printability, solvent resistance, melt strength, miscibilitywith other polymers, and gas barrier properties, as compared tounfunctionalized polyolefins.

[0007] ExxonMobil currently sells ester—(Optema™, Enable™),acetate—(Escorene™), and acid/ionomer—functionalized polyethylenes(Escor™, Iotek™) made by free-radical processes for adhesive, film, andspecialty applications, among others.

[0008] However, free-radical polymerization methods do not allow for theprecise control of important polymer properties such as branching,tacticity, molecular weight and molecular weight distribution. For thisreason, it is desirable to develop transition metal catalysts capable ofcarrying out the direct copolymerization of olefins with polarcomonomers. Market opportunities and advantages for substantially linearfunctional polyolefins and other controlled structures are expected inareas such as recreational materials (golf ball covers), durable goods,packaging, adhesives, and alloys.

[0009] To date, few systems for the direct copolymerization of olefinsand polar comonomers exist. Cationic Pd diimine initiators, developed byBrookhart/DuPont, are capable of producing polyethylenes with up to ˜20mol % incorporation of acrylate comonomer. However, these materials arevery heavily branched, and the acrylate comonomer is overwhelminglyplaced at the ends of branches rather than in the main chain (WO96/23010; J. Am. Chem. Soc. 1996, 118, 267; J. Am. Chem. Soc. 1998, 120,888). Modified versions of these Pd diimines, and related P—O ligated Pdcomplexes (developed by Drent), can give more linear copolymers but atthe expense of greatly reducing comonomer incorporation (<2 mol %) (WO2001/92342; Polym. Mat. Sci. Eng. 2002, 86, 319; Polym. Mat. Sci. Eng.2002, 86, 322; Chem. Commun. 2002, 744; Organometallics 2002, 21, 2836).To date, the most versatile copolymerization catalysts reported areGrubbs' single-component imine-phenoxide “neutral nickel” initiators.These salicylaldimine-ligated complexes can produce relatively linearcopolymers of ethylene with functionalized long-chain and norbornenecomonomers, having polar incorporations of up to ˜30 mol %.

[0010] Recently, ExxonMobil developed a proprietary single-componentneutral nickel olefin polymerization catalyst havingo-aryl-disubstituted azo-phenoxide ligands (U.S. Ser. No. 10/436,741,filed May 13, 2003). This initiator can produce higher molecular weightpolyethylenes and ethylene-octene copolymers than the relatedimine-phenoxide nickel initiators of Grubbs (which are reported tocatalyze copolymerization of olefins with certain polar comonomers).Herein we report a process for the direct copolymerization of ethylene(or other olefins) with functionalized comonomers using our novelcatalyst compounds. This catalyst shows certain advantages over theimine-phenoxide nickel initiators, including greater retention ofcatalyst activity and molecular weight in the presence of functionalgroups, and greater copolymer linearity or polar comonomer incorporationunder certain conditions.

[0011] Additional references of interest involving ethylene/polarcomonomer copolymerizations include: U.S. Pat. No. 6,410,664; U.S. Pat.No. 6,143,857; U.S. Pat. No. 6,562,922; Ittel, S. D. et al., Chem. Rev.2000, 100, 1169; Gibson, V. C. et al., Chem. Rev. 2003, 103, 283; DD99556 (East German patent); U.S. Pat. No. 6,506,704, WO 00/56785; U.S.Pat. No. 6,197,715; U.S. Pat. No. 6,197,714; Stibrany, R. T. et al.,Macromolecules 2003, 36, 8584; WO 99/30822; U.S. Pat. No. 6,037,297;U.S. Pat. No. 6,417,303; U.S. Pat. No. 6,180,788; Stibrany, R. T. etal., Polymeric Materials: Science & Engineering 2002, 86, 325; andStibrany, R. T. et al., in Beyond Metallocenes: Next-GenerationPolymerization Catalysts; Patil, A. O.; Hlatky, G. G., Eds.; ACSSymposium Series 857; American Chemical Society: Washington, D.C., 2003,222.

SUMMARY OF THE INVENTION

[0012] This invention relates to a polymerization method comprisingcontacting one or more polar monomers and one or more olefin monomerswith a catalyst system comprising: 1) optionally, an activator, and 2) acatalyst composition represented by the formula:

[0013] M is selected from groups 3-11 of the periodic table;

[0014] E is nitrogen or phosphorus;

[0015] Ar⁰ is arene;

[0016] R¹-R⁴ are, each independently, selected from hydrogen,hydrocarbyl, substituted hydrocarbyl or functional group, providedhowever that R³ and R⁴ do not form a naphthyl ring;

[0017] L¹ represents a formal anionic ligand,

[0018] L² represents a formal neutral ligand,

[0019] a is an integer greater than or equal to 1;

[0020] b is an integer greater than or equal to 0; and

[0021] c is an integer greater than or equal to 1.

DETAILED DESCRIPTION OF THE INVENTION

[0022] For the purposes of this invention and the claims thereto when apolymer is referred to as comprising a monomer, the momomer present inthe polymer is the polymerized form of the monomer. For the purposes ofthis invention and the claims thereto when a polymer is referred to ascomprising an olefin, the olefin present in the polymer is thepolymerized form of the olefin. For the purposes of this invention andthe claims thereto when a polymer is referred to as comprising a polarmonomer, the polar monomer present in the polymer is the polymerizedform of the polar monomer. In the description herein the transitionmetal catalyst compound may be described as a catalyst precursor, apre-catalyst compound, a transition metal complex or a catalystcompound, and these terms are used interchangeably. A catalyst system isa combination of a transition metal catalyst compound and an activator.An activator is also interchangeably referred to as a cocatalyst. Inaddition, a reactor is any container(s) in which a chemical reactionoccurs.

[0023] As used herein, the numbering scheme for the Periodic TableGroups is the new notation as described in CHEMICAL AND ENGINEERINGNEWS, 63(5), 27 (1985).

[0024] Further for purposes of this invention Me is methyl, Ph isphenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normalpropyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu ispara-tertiary butyl, and TMS is trimethylsilyl.

[0025] The catalyst compound preferably contains at least oneE-phenoxide ligand (L⁰), and at least one formal neutral ligand (L²).The remaining ligands in the coordination sphere of the metal compoundtypically are such that the compound attains a d electron count of14-18. The d electron count is the formal sum of the metal's d electronsplus those contributed by the ligands.

[0026] Preferred E-phenoxide metal compounds are represented by formula:

[0027] wherein:

[0028] M is selected from groups 3-11 of the periodic table, preferablygroup 4 or 10, more preferably Ti or Ni;

[0029] L⁰ represents an E-phenoxide ligand represented by the formula:

[0030] wherein:

[0031] E is nitrogen or phosphorus, preferably nitrogen;

[0032] Ar⁰ is arene;

[0033] R¹-R⁴ are each independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl or functional group, provided that R³ and R⁴ donot form a naphthyl ring;

[0034] L¹ represents a formal anionic ligand;

[0035] L² represents a formal neutral ligand;

[0036] a is an integer greater than or equal to 1, preferably a=1, 2, 3or 4, preferably a 1 or 2;

[0037] b is an integer greater than or equal to 0, preferably b is 0, 1,2, 3, 4, 5 or 6, more preferably b=0, 1 or 2; and

[0038] c is an integer greater than or equal to 1, preferably c=1, 2, 3or 4, more preferably 1 or 2.

[0039] The metal compound may be neutral or a charged species with acounterion.

[0040] The metal compound preferably contains at least one formalneutral ligand coordinated to the metal in addition to the nitrogen orphosphorus of the E-phenoxide ligand(s). Formal neutral ligands aredefined as ligands that are neutral, with respect to charge, whenformally removed from the metal in their closed shell electronic state.Formal neutral ligands contain at least one lone pair of electrons,pi-bond or sigma bond that are capable of binding to the transitionmetal. Formal neutral ligands may also be polydentate when more than oneformal neutral ligand is connected via a bond or a hydrocarbyl,substituted hydrocarbyl or a functional group tether. A formal neutralligand may be a substituent of another metal compound, either the sameor different, such that multiple compounds are bound together.

[0041] Formal neutral ligands may be composed of combinations ofhydrocarbyl, substituted hydrocarbyl, and functional groups.Non-limiting examples of formal neutral ligands are ethers, ketones,esters, alcohols, carboxylic acids, amines, imines, azo, nitriles,heterocycles, phosphines, thioethers, alkyls, alkenes, alkynes, andarenes.

[0042] For purposes of this invention and the claims thereto “ZETAFORMAL NEUTRAL LIGANDS” are defined to be formal neutral ligandsrepresented by the following formulae:

[0043] P(C(CH₃)₃)₃ P(C₆H₁₁)₃ P(CH(CH₃)₂)₃ P(CH₂CH₂CH₃)₃ P(CH₂CH₃)₃P(CH₃)₃ P(C₆H₄OCH₃)₃ P(CH₂C₆H₅)₃ P(C₆H₄CH₃) P(C₆H₅)₃ P(CH═CH₂)₃P(C₆H₄F)₃ P(C₆H₄Cl)₃ P(C₂H₅)₂C₆H₅ P(CH₃)₂C₆H₅ P(C₆H₅)₂CH₃ P(C₆H₅)₂NMe₂P(C₆H₅)CH₂C₆H₅ P(C₆H₅)₂(C₆H₄OCH₃) P(C₆H₅)(CH₂ C₆H₅)₂ P(C₆H₅)₂(C H═CH₂)P(C₆H₅)₂(C₆H₄F) P(OCH₂CH₃)(C₆H₅)₂ P(OCH(CH₃)₂)₂C₆H₅ PH(C₆H₅)₂P(OCH₂CH₂CH₃)₂C₆H₅ P(OC₆H₅)(C₆H 5)₂ P(C₆H₅)₂C₆ F₅ PPh₂ (C₆H₄Cl)P(C₆H₃(OCH₃)₂)₃ P(C₆H₅)₂(C₆H₄N(CH₃)₂) P(C₆H₂(CH₃)₃)₃P(C₆H₅)₂(C₆H₂(CH₃)₃) P(C₆H₅)(C₆ F₅)₂ P(C₆F₅)₃ P(C₁₀H₇)₃ Me₃P═CH₂(C₆H₅)₃P═CH₂ H₂C═CH₂ H₂C═CHCH₃ H₂C═CH₂CH₂CH₃ CH₃CH═CHCH₃H₂C═CH₂CH₂CH₂CH₃ CH₃CH═CHCH₂CH₃ H₂C═CH₂CH₂CH₂CH₂CH₃ CH₃CH═CHCH₂CH₂CH₃CH₃CH₂CH═CHCH₂CH₃ CH₃CH═CHCH₂CH₂CH₂CH₂CH₃ C H₃CH₂CH═CHCH₂CH₂CH₂CH₃H₂C═CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃CH₂CH₂CH═CHCH₂CH₂CH₃ CH₃CH(CH₃)CH═CH₂C(CH₃)₃CH═CH₂ (CH₃)₂C═CH₂ CH₃CH₂CH(CH₃)CH═CH₂ H₂C═CH.CH═CH₂CH₃CH═CH.CH═CH₂ CH₃CH═CH.CH═CHCH₃ H₂C═C(CH₃)—(CH₃)C═CH₂ (CH₃CH₂)₂C═CH₂H₂C═C(CH₃)—CH═CH₂ H₂C═CH—CH₂)₁—CH═CH₂ H₂C═CH—CH₂)₂—CH═CH₂H₂C═CH—CH₂)₃—CH═CH₂ H₂C═CH—CH₂)₄—CH═CH₂ H₂C═CH—CH₂)₁—CH═C(CH₃)₂H₂C═CH—CH₂)₂—CH═C(CH₃)₂ H₂C═CH—CH₂)₃—CH═C(CH₃)₂ H₂C═CH—CH₂)₄—CH═C(CH₃)₂(C₆H₅)CH═CH—CH═CH₂ (C₆H₅)CH═CH—CH═CH(C₆H₅) CH₂═CH—CH₂CH═CHCH₃CH₂═CH—CH₂C(CH₃)═CHCH₃ CH₂═C(CH₃)—CH₂CH═CHCH₃ CH₂═C(CH₃)—CH₂CH₃ CHCH₃HC═C H₂CH═CHCH₂CH₃

[0044] CH₃OCH₃ CH₃CH₂OCH₂CH₃

[0045] CH₃C(O)CH₃ CH₃C(O)OCH₃ NC—CH₃ NC—C₆H₅ NC—C₆F₅ NC—C₆H₃(CF₃)₂N(CH₃)₂C₆H₅ N(CH₂CH₃)₂C₆H₅

[0046] Formal anionic ligands are defined as ligands that are anionic,with respect to charge, when formally removed from the metal in theirclosed shell electronic state. Formal anionic ligands include hydride,halide, hydrocarbyl, substituted hydrocarbyl or functional group.Non-limiting examples of formal anionic ligands include hydride,fluoride, chloride, bromide, iodide, alkyl, aryl, alkenyl, alkynyl,allyl, benzyl, acyl, trimethylsilyl. Formal anionic ligands may also bepolydentate when more than one formal anionic ligand is connected via abond or a hydrocarbyl, substituted hydrocarbyl or a functional grouptether. A formal anionic ligand may be a substituent of another metalcompound, either the same or different, such that multiple compounds arebound together.

[0047] For purposes of this invention and the claims thereto“ZETA-FORMAL ANIONIC LIGANDS” is defined to be the group of formalanionic ligands represented by the following formulae:

[0048] —F —Cl —Br —I —CN —NO₂ —N(CH₃)₂ —N(CH₂CH₃)₂ —N(Si(CH₃)₃)₂—N(CH₃)(Si(CH₃)₃) —OC(O)CH₃ —OC(O)CF₃ —S(O)₂CH₃ —OS(O)₂CH₃—OS(O)₂C₆H₄CH₃—OS(O)₂CF₃ —OS(O)₂C₆H₄NO₂ —OS(O)₂C₄F₉ —OS(O)₂C₆H₄Br —SC₆H₅

[0049] —N═N—C₆H₅ —OCH₃ —OCH₂CH₃ —OC(CH₃)₂H —O(CH₃)₃ —CF₃ —C(O)H —C(O)CH₃—H —CH₃ —CH₂CH₃ —CH(CH₃)₂ —C(CH₃)₃ —CH═CH₂ —C≡CH —CH₂C₆H₅ —CH₂Si(CH₃)₃—C₆H₅ —C₁₀H₇ —CH₂C(CH₃)₃ —CH₂CH₂C(CH₃)₃

[0050] More preferred formal anionic ligands include: —F, —Cl, —Br, —I,—N(CH₃)₂, —OCH₃, —H, —CH₃, —C₆H₅, -allyl, -benzyl, —CH₂Si(CH₃)₃.

[0051] Preferred non-limiting examples of formal anionic ligand thatcomprises a functional group include:

[0052] —F —Cl —Br —I —CN —NO₂ —N(CH₃)₂ —N(CH₂CH₃)₂ —N(Si(CH₃)₃)₂—N(CH₃)(Si(CH₃)₃) —OC(O)CH₃ —OC(O)CF₃ —S(O)₂CH₃ —OS(O)₂CH₃—OS(O)₂C₆H₄CH₃—OS(O)₂CF₃ —OS(O)₂C₆H₄NO₂ —OS(O)₂C₄F₉ —OS(O)₂C₆H₄Br —SC₆H₅

[0053] —N═N—C₆H₅ —OCH₃ —OCH₂CH₃ —OC(CH₃)₂H —O(CH₃)₃

[0054] More preferred formal anionic ligands that comprise functionalgroups include: —F, —Cl, —Br, —I, —N(CH₃)₂, —OCH₃.

[0055] Using this nomenclature of anionic and neutral ligands, theligands may be categorized as combinations of anionic and neutralligands as when L¹ and L² are connected via a bond or a hydrocarbyl,substituted hydrocarbyl or a functional group tether. Preferrednon-limiting examples of L¹, L² that meet this definition include ethyl,norbornyl, allyl, benzyl, CH₂CH₂C(O)Me, 1-(2-N(CH₃)₂C₆H₄),acetylacetonate. The capability of hydrocarbyl groups, such as ethyl andnorbornyl, to coordinate as a formal anionic ligand (M-C sigma bond) anda formal neutral ligand, via an agostic 3 center-2 electron interactionbetween C, H and M is well recognized.

[0056] Monodentate ligands that are capable of multiple bonding to themetal may be categorized as combinations of anionic and neutral ligands.Ligands which display this behavior are functional groups that inaddition to being a formal anionic ligand, have at least one pair ofelectrons, either localized or in a bonding arrangement with anotheratom or atoms, that also interact with the metal.

[0057] Non-limiting examples of such ligands are oxo, imido, carbene andcarbyne. Preferred non-limiting examples include:

[0058] ═O ═CPh₂ ═CH₂ ═CHPh ═CH(C₆H₂(CH₃)₃) ≡C—C₆H₂(CH₃)₃ ≡C—C₆H₃(CH(CH₃)₂ ≡N—C₆H₂(C H₃)₃ ≡N—C₆H₃(CH(CH₃)₂

[0059] Preferred non-limiting examples of hydrocarbyl groups include:

[0060] —H —CH₃ —CH₂CH₃ —CH(CH₃)₂ —C(CH₃)₃ —CH═CH₂ —C≡CH —CH₂C₆H₅—CH₂Si(CH₃)₃ —C₆H₅ —C₁₀H₇ —CH₂C(CH₃)₃ —CH₂CH₂C(CH₃)₃

[0061] Substituted hydrocarbyl radicals (also called substitutedhydrocarbyls) are radicals in which at least one hydrocarbyl hydrogenatom has been substituted with at least one heteroatom or heteroatomcontaining group.

[0062] Preferred non-limiting examples of substituted hydrocarbylsinclude:

[0063] —CH₂OH —C(O)H —CO₂H —CH₂OCH₃

[0064] —CH₂N(CH₃)₂

[0065] —CH₂Cl —CN

[0066] The term “hydrocarbyl radical” is sometimes used interchangeablywith “hydrocarbyl” throughout this document. For purposes of thisdisclosure, “hydrocarbyl radical” encompasses radicals containing carbonhydrogen and optionally silicon atoms, preferably 1 to 100 carbon atoms,hydrogen and optionally silicon. These radicals can be linear, branched,or cyclic including polycyclic. These radicals can be saturated,partially unsaturated or fully unsaturated, and when cyclic, may bearomatic or non-aromatic.

[0067] In some embodiments, the hydrocarbyl radical is selected frommethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl,tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl,nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl,tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl,nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl,tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl,nonacosynyl, or triacontynyl isomers. For this disclosure, when aradical is listed it indicates that radical type and all other radicalsformed when that radical type is subjected to the substitutions definedabove. Alkyl, alkenyl and alkynyl radicals listed include all isomersincluding where appropriate cyclic isomers, for example, butyl includesn-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

[0068] An arene is a substituted or unsubstituted aromatic hydrocarbon.Arenes may be monocyclic, polycyclic, hydrocarbon ring assemblies orfused ring systems. Arenes may be substituted or unsubstitutedheterocyclics, polyheterocyclics, heterocyclic ring assemblies or fusedheterocyclic ring systems. (In the formulae below, Z⁺ is a cation,preferably a metal or metal compound of groups 1, 2, 11, or 12 and A⁻ isan anion.) For purposes of this invention and the claims thereto theterm “ZETA-ARENES” is defined to be the group of arenes represented bythe following formulae:

[0069] Functional groups are heteroatoms of groups 1-17 of the periodictable either alone or connected to other elements by covalent or otherinteractions such as ionic, van der Waals forces, or hydrogen bonding.Examples of functional groups include carboxylic acid, acid halide,carboxylic ester, carboxylic salt, carboxylic anhydride, aldehyde andtheir chalcogen (Group 14) analogues, alcohol and phenol, ether,peroxide and hydroperoxide, carboxylic amide, hydrazide and imide,amidine and other nitrogen analogues of amides, nitrile, amine andimine, azo, nitro, other nitrogen compounds, sulfur acids, seleniumacids, thiols, sulfides, sulfoxides, sulfones, phosphines, phosphates,other phosphorus compounds, silanes, boranes, borates, alanes,aluminates. Functional groups may also be taken broadly to includeorganic polymer supports or inorganic support material such as alumina,and silica.

[0070] The nomenclature of d electron count, anionic ligands, neutralligands, and oxidation state used here are described in length in thetexts: Hegedus, L. S. Transition Metals in the Synthesis of ComplexOrganic Molecules 2nd Ed, University Science Press, 1999, Sausalito,Calif. and Collman, J. P. et. al. Principles and Applications ofOrganotransition Metal Chemistry. University Science Press, 1987,Sausalito, Calif.

[0071] Preferred E-phenoxide metal compounds include those representedby the following formulae: (L⁰)_(a)(L¹)_(b-2)(L²)_(c)M(R⁵)₂(L⁰)_(a)(L¹)_(b-2)(L²)_(c)M(R⁵)₁(L³)₁ (L⁰)_(a)(L¹)_(b-2)(L²)_(c)M(L³)₂ 23 4 (L⁰)_(a)(L²)_(c)M (L⁰)_(a)(L¹)_(b-1)(L²)_(c)M(R⁵)₁(L⁰)_(a)(L¹)_(b-1)(L²)_(c)M(L³)₁ 5 6 7

[0072] wherein:

[0073] M is selected from groups 3-11 of the periodic table, preferablygroup 4 or 10, more preferably Ti or Ni.

[0074] L⁰ represents an E-phenoxide ligand represented by the formula:

[0075] L¹ represents a formal anionic ligand;

[0076] L² represents a formal neutral ligand;

[0077] L³ represents a formal anionic ligand that comprises a functionalgroup;

[0078] a is greater than or equal to 1, preferably a=1, 2, 3 or 4,preferably a=1 or 2;

[0079] b is greater than or equal to 0, preferably b is 0, 1, 2, 3, 4, 5or 6, more preferably b=0, 1 or 2, provided that b is not 0 or 1 informula 2, 3 or 4 and b is not 0 in formula 6 or 7;

[0080] c is greater than or equal to 1, preferably c=1, 2, 3 or 4, morepreferably 1 or 2;

[0081] E is nitrogen or phosphorus, preferably nitrogen;

[0082] N is nitrogen;

[0083] O is oxygen;

[0084] Ar⁰ is an arene;

[0085] R¹-R⁴ are each independently hydrogen, a hydrocarbyl, asubstituted hydrocarbyl or a functional group, provided that R³ and R⁴do not form a naphthyl ring; and

[0086] R⁵ is a hydride, a hydrocarbyl or a substituted hydrocarbyl.

[0087] Additional preferred E-phenoxide metal compounds include thoserepresented by the following formulae:

[0088] E is nitrogen or phosphorus, preferably nitrogen;

[0089] N is nitrogen;

[0090] O is oxygen

[0091] Ar¹ is arene; preferably one or more of:

[0092] R¹-R⁴ are each independently hydrogen, a hydrocarbyl, asubstituted hydrocarbyl or a functional group, provided that R³ and R⁴do not form a naphthyl ring;

[0093] L¹ represents a formal anionic ligand;

[0094] L² represents a formal neutral ligand;

[0095] “d” equals 1, 2 or 3, preferably 2;

[0096] A⁻ is an anion that may or may not coordinate to Ni or maycoordinate weakly to N; A⁻ may be a non-coordinating anion, asubstituted hydrocarbon or a functional group, preferably A⁻ comprisesone or more halides, carboxylates, phosphates, sulfates, sulfonates,borates, aluminates, alkoxides, thioalkoxides, anonic substitutedhydrocarbons, or anionic metal complexes;

[0097] Z⁺ is a cation, preferably a metal or metal complex of groups 1,2, 11, or 12.

[0098] Preferably, the metal compound contains at least one formalneutral ligand coordinated to the metal in addition to the nitrogen orphosphorus of the E-phenoxide ligand(s).

[0099] The nickel compounds contain one E-phenoxide ligand and at leastone formal neutral ligand. The remaining ligands in the coordinationsphere of the metal compound are such that the compound attains a delectron count of 14-18. The nickel compound may be neutral or a chargedspecies with an appropriate counterion.

[0100] Preferred metal compounds include those containing oneazo-phenoxide ligand, one formal neutral ligand, and one formal anionicligand.

[0101] Additional preferred azo-phenoxide metal compounds arerepresented by formula 11 and its steroisomers:

[0102] L¹ represents a formal anionic ligand;

[0103] R³ is hydrogen, a hydrocarbyl, a substituted hydrocarbyl or afunctional group;

[0104] R⁶ is C(R⁷)_(e), e=2 or 3, R⁷ is a hydrocarbon, a substitutedhydrocarbon, or a functional group, two R⁷ groups may be part of acommon arene ring when e=2; Preferred non-limiting examples of R⁶include t-butyl, adamantyl, phenyl, naphthyl, anthracenyl.

[0105] Ar¹ is an arene;

[0106] L⁴, is a formal neutral ligand, coordinated to the nickel inaddition to the nitrogen of the azo-phenoxide ligand, based on carbon,nitrogen or phosphorus, preferably one or more alkenes, alkynes,nitriles, pyridines, aryl phosphines and phosphorus ylides. Non-limitingpreferred examples of L⁴ include:

[0107] P(C₆H₅)₃ P(C₁₀H₇)₃ NC—CH₃ NC—C₆H₃(CF₃)₂ CH₂═CH₂

[0108] Particularly preferred azo-phenoxide compounds are represented byformula 12:

[0109] wherein:

[0110] L⁴ represents a formal neutral ligand based on carbon, nitrogenor phosphorus preferably one or more alkenes, alkynes, nitriles,pyridines, aryl phosphines and or phosphorus ylides;

[0111] R⁸ represents a formal anionic ligand which may be hydrogen or ahydrocarbon, preferably a hydride, methyl, ethyl, trimethylsilylmethyl,trimethylsilyl, phenyl, naphthyl, allyl, benzyl;

[0112] Ar² is a phenyl group substituted in the 2 and 6 positions by 2°hydrocarbons, 2° substituted hydrocarbons, 3° hydrocarbons, 3°substituted hydrocarbons, or arenes;

[0113] Me is methyl.

[0114] Preferred non-limiting examples of Ar² include:

[0115] For purposes of this invention, where the terms 2° and 3° areused we mean that the hydrocarbon is 2° or 3° prior to substitution ontothe arene ring. For example in the structures above the iPr is 2° andthe tBu is 3°.

[0116] Ar³ is an arene. Preferred non-limiting examples of Ar³ include:

[0117] In another preferred embodiment the catalyst compounds describedherein may be used in combination with other polymerization and oroligomerization catalysts. In a preferred embodiment the instantcatalyst compounds are used in combination with catalyst compoundsdescribed in any of the following references:

[0118] 1. Younkin, T. R.; Connor, E. F.; Henderson, J. I.; Friederich,S. K.; Grubbs, R. H.; Bansleben, D. A. Science 2000, 287, 460

[0119] 2. Wang, C. Friederich, S.; Younkin, T. R.; Li, R. T.; Grubbs, R.H.; Bansleben, D. A.; Day, M. W. Organometallics 1998, 17, 3149

[0120] 3. Johnson, L. K.; Bennett, A. M. A.; Wang, L.; Parthasarathy,A.; Hauptman, E.; Simpson, R. D.; Feldman, J.; Coughlin, E. B. WO98/30609

[0121] 4. Bansleben, D. A.; Friederich, S. K.; Younkin, T. R.; Grubbs,R. H.; Wang, C.; Li, R. T. WO 98/42664

[0122] 5. Bansleben, D. A.; Friederich, S. K.; Younkin, T. R.; Grubbs,R. H.; Wang, C.; Li, R. T. WO 98/42665

[0123] 6. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Henderson, J.I.; Younkin, T. R.; Nadjadi, A. R. WO 2000/56786

[0124] 7. Bansleben, D. A.; Connor, B. F.; Grubbs, R. H.; Henderson, J.I.; Younkin, T. R.; Nadjadi, A. R. WO 2000/56787

[0125] 8. Bansleben, D. A.; Friedrich, S. K.; Grubbs, R. H.; Li, R. T.;Connor, E. F.; Roberts, W. P. WO 2000/56781

[0126] 9. Hicks, F.; Brookhart, M. Organometallics 2001, 20, 3217

[0127] 10. Connor, E. F.; Younkin, T. R.; Henderson, J. I.; Hwang, S.;Grubbs, R. H.; Roberts, W. P.; Litzau, J. J. J. Polym. Sci. A 2002, 40,2842

[0128] 11. Schroeder, D. L.; Keim, W.; Zuideveld, M. A.; Mecking, S,Macromolecules, 2002, 35, 6071

[0129] 12. Matsui, S.; Nitabaru, M.; Tsuru, K.; Fujita, T.; Suzuki, Y.;Takagi, Y.; Tanaka, H. EP 0 990 664 A1

[0130] 13. Laali, K.; Szele, I.; Zollinger, H., Helvetica Chimica Acta1983, 66, 1737

[0131] 14. Petrillo, G.; Novi, M.; Garbarino, G.; Filiberti, M.,Tetrahedron 1989, 45, 7411

[0132] 15. Johnson, L. K.; Killian, C. M.; Arthur, S. D.; Feldman, J.;McCord, E. F.; McLain, S. J.; Kreutzer, K. A.; Bennett, M. A.; Coughlin,E. B.; Ittel, S. D.; Parthasarathy, A.; Tempel, D.; Brookhart, M. S. WO96/23010

[0133] 16. Johnson, L. K.; Mecking, S.; Brookhart, M. J. Am. Chem. Soc.1996, 118,

[0134] 17. Mecking, S.; Johnson, L. K.; Wang, L.; Brookhart, M. J. Am.Chem. Soc. 1998, 120, 888

[0135] 18. Wang, L.; Hauptman, E.; Johnson, L. K.; McCord, E. F.; Wang,Y.; Ittel, S. D. WO 01/92342

[0136] 19. Johnson, L.; Bennett, A.; Dobbs, K.; Hauptman, E.; lonkin,A.; Ittel, S.; McCord, E.; McLain, S.; Radzewich, C.; Yin, Z.; Wang, L.;Wang, Y.; Brookhart, M. Polym. Mat. Sci. Eng. 2002, 86, 319

[0137] 20. Wang, L.; Hauptman, E.; Johnson, L. K.; Marshall, W. J.;McCord, E. F.; Wang, Y.; Ittel, S. D.; Radzewich, C. E.; Kunitsky, K.;lonkin, A. S. Polym. Mat. Sci. Eng. 2002, 2002, 322

[0138] 21. Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh,R. I. Chem. Commun. 2002, 744

[0139] 22. Liu, W.; Malinoski, J. M.; Brookhart, M. Organometallics2002, 21, 2836

[0140] 23. Bansleben, D. A.; Friedrich, S. K.; Younkin, T. R.; Grubbs,R. H.; Wang, C.; Li, R. T. U.S. Pat. No. 6,410,664

[0141] 24. Bansleben, D. A.; Friedrich, S. K.; Grubbs, R. H.; Li, R. T.;Wang, C.; Younkin, T. R. U.S. Pat. No. 6,143,857

[0142] 25. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Roberts, W.P. U.S. Pat. No. 6,562,922

[0143] 26. Mix, H.; Kurras, E.; Wilcke, F.-W.; Reihsig, J.; Schulz, W.;Fuhrmann, H.; Grassert, I.; Fuchs, W.; Meissner, J. DD 99556 Aug. 12,1973

[0144] 27. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Henderson, J.I.; Younkin, T. R. U.S. Pat. No. 6,506,704

[0145] 28. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Henderson, J.I.; Younkin, T. R. WO 00/56785

[0146] 29. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Henderson, J.I.; Nadjadi, A. R. Jr.; Younkin, T. R. U.S. Pat. No. 6,197,715

[0147] 30. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Henderson, J.I.; Nadjadi, A. R. Jr.; Younkin, T. R. U.S. Pat. No. 6,197,714

[0148] 31. Stibrany, R. T.; Schulz, D. N.; Kacker, S.; Patil, A. O.;Baugh, L. S.; Rucker, S. P.; Zushma, S.; Berluche, E.; Sissano, J. A.Macromolecules 2003, 36, 8584

[0149] 32. Stibrany, R. T.; Schulz, D. N.; Kacker, S.; Patil, A. O. PCTInt. Appl. WO 99/30822 (Exxon), 1999

[0150] 33. Stibrany, R. T.; Schulz, D. N.; Kacker, S.; Patil, A. O. U.S.Pat. No. 6,037,297 (Exxon), 2000

[0151] 34. Stibrany, R. T.; Schulz, D. N.; Kacker, S.; Patil, A. O. U.S.Pat. No. 6,417,303 (ExxonMobil), 2002

[0152] 35. Stibrany, R. T. U.S. Pat. No. 6,180,788 (Exxon), 2001

[0153] 36. Stibrany, R. T.; Schulz, D. N.; Kacker, S.; Patil, A. O.;Baugh, L. S.; Rucker, S. P.; Zushma, S.; Berluche, E.; Sissano, J. A.Polymeric Materials: Science & Engineering 2002, 86, 325

[0154] 37. Stibrany, R. T.; Schulz, D. N.; Kacker, S.; Patil, A. O.;Baugh, L. S.; Rucker, S. P.; Zushma, S.; Berluche, E.; Sissano, J. A. InBeyond Metallocenes: Next-Generation Polymerization Catalysts; Patil, A.O.; Hlatky, G. G., Eds.; ACS Symposium Series 857; American ChemicalSociety: Washington, D.C., 2003, 222.

[0155] Activators and Activation Methods for Catalyst Compounds

[0156] An activator is defined as any combination of reagents thatincreases the rate at which a metal compound, containing at least oneE-phenoxide ligand and one formal neutral ligand, oligomerizes orpolymerizes unsaturated monomers. An activator may also affect themolecular weight, degree of branching, comonomer content, or otherproperties of the oligomer or polymer. The E-phenoxide compoundsaccording to the invention may be activated for oligomerization and orpolymerization catalysis in any manner sufficient to allow coordinationor cationic oligomerization and or coordination or cationicpolymerization.

[0157] Generally speaking, successful oligomerization and/orpolymerization catalysts contain a formal anionic ligand, such ashydride or hydrocarbyl, with an adjacent (cis) coordination siteaccessible to an unsaturated monomer. Coordination of an unsaturatedmonomer to the cis coordination site allows a migratory insertionreaction to form a metal alkyl. Repetition of this process causes chaingrowth. An activator is thus any combination of reagents thatfacilitates formation of a transition metal compound containing, inaddition to at least one E-phenoxide ligand, cis coordinated olefin andhydride or hydrocarbyl.

[0158] When the E-phenoxide compound contains at least one hydride orhydrocarbyl ligand, activation can be achieved by removal of formalanionic or neutral ligands, of higher binding affinity than theunsaturated monomer. This removal, also called abstraction, process mayhave a kinetic rate that is first-order or non-first order with respectto the activator. Activators that remove formal anonic ligands aretermed ionizing activators. Activators that remove formal neutralligands are termed non-ionizing activators. Activators are typicallystrong Lewis-acids which may play either the role of ionizing ornon-ionizing activator.

[0159] When the E-phenoxide compound does not contain at least onehydride or hydrocarbyl ligands, then activation may be a one step ormulti step process. A step in this process includes coordinating ahydride or hydrocarbyl group to the metal compound. A separateactivation step is removal of formal anionic or neutral ligands ofhigher binding affinity than the unsaturated monomer. These activationsteps may occur in series or in parallel. These steps may occur in thepresence of unsaturated monomers or these steps may occur prior toexposure to the monomers. More than one sequence of activation steps ispossible to achieve activation.

[0160] The activator may also act to coordinate a hydride or hydrocarbylgroup to the metal compound, containing at least one E-phenoxide ligandand one formal neutral ligand. When the E-phenoxide compound does notcontain at least one hydride or hydrocarbyl ligands but does contain atleast one functional group ligand, activation may be effected bysubstitution of the functional group with a hydride, hydrocarbyl orsubstituted hydrocarbyl group. This substitution may be effected withappropriate hydride or alkyl reagents of group 1, 2, 12, 13 elements asis known in the art. To achieve activation, it may be necessary to alsoremove formal anionic or neutral ligands of higher binding affinity thanthe unsaturated monomer.

[0161] Alumoxane and aluminum alkyl activators are capable of alkylationand abstraction activation.

[0162] The activator may also act to coordinate a hydride or hydrocarbylgroup to the metal compound, containing at least one E-phenoxide ligandand one formal neutral ligand. If the E-phenoxide compound does notcontain formal anionic ligands, then a hydride, hydrocarbyl orsubstituted hydrocarbyl may be coordinated to a metal usingelectrophilic proton or alkyl transfer reagents represented byH⁺(LB)_(n)A⁻, (R⁹)⁺(LB)_(n)A⁻. R⁹ is a hydrocarbyl or a substitutedhydrocarbyl; LB is a Lewis-base, n=0, 1 or 2. Non-limiting examples ofpreferred Lewis-bases are diethyl ether, dimethyl ether, ethanol,methanol, water, acetonitrile, N,N-dimethylaniline. A⁻ is an anionpreferably a substituted hydrocarbon, a functional group, or anon-coordinating anion. Non-limiting examples of A⁻ include halides,carboxylates, phosphates, sulfates, sulfonates, borates, aluminates,alkoxides, thioalkoxides, anionic substituted hydrocarbons, and anionicmetal complexes.

[0163] A. Alumoxane and Aluminum Alkyl Activators

[0164] In one embodiment, one or more alumoxanes are utilized as anactivator in the catalyst composition of the invention. Alumoxanes,sometimes called aluminoxanes in the art, are generally oligomericcompounds containing —Al(R)—O— subunits, where R is an alkyl group.Examples of alumoxanes include methylalumoxane (MAO), modifiedmethylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.Alkylalumoxanes and modified alkylalumoxanes are suitable as catalystactivators, particularly when the abstractable ligand is a halide.Mixtures of different alumoxanes and modified alumoxanes may also beused. For further descriptions, see U.S. Pat. Nos. 4,665,208, 4,952,540,5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018,4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137,5,103,031 and EP 0 561 476 A1, EP 0279 586 B1, EP 0 516 476 A, EP 0 594218 A1 and WO 94/10180.

[0165] When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst precursor (per metal catalytic site). Theminimum activator-to-catalyst-precursor is typically a 1:1 molar ratio.

[0166] Alumoxanes may be produced by the hydrolysis of the respectivetrialkylaluminum compound. MMAO may be produced by the hydrolysis oftrimethylaluminum and a higher trialkylaluminum such astriisobutylaluminum. MMAO's are generally more soluble in aliphaticsolvents and more stable during storage. There are a variety of methodsfor preparing alumoxane and modified alumoxanes, non-limiting examplesof which are described in U.S. Pat. Nos. 4,665,208, 4,952,540,5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463,4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137,5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451,5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and Europeanpublications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0586 665, and PCT publications WO 94/10180 and WO 99/15534, all of whichare herein fully incorporated by reference. It may be preferable to usea visually clear methylalumoxane. A cloudy or gelled alumoxane can befiltered to produce a clear solution or clear alumoxane can be decantedfrom the cloudy solution. Another preferred alumoxane is a modifiedmethyl alumoxane (MMAO) cocatalyst type 3A (commercially available fromAkzo Chemicals, Inc. under the trade name Modified Methylalumoxane type3A, covered under patent number U.S. Pat. No. 5,041,584).

[0167] Aluminum alkyl or organoaluminum compounds which may be utilizedas activators (or scavengers) include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

[0168] B. Ionizing Activators

[0169] It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri(n-butyl)ammoniumtetrakis (pentafluorophenyl)boron, a trisperfluorophenyl boron metalloidprecursor or a trisperfluoronaphthyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof. It is also within the scope ofthis invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

[0170] Examples of neutral stoichiometric activators includetri-substituted boron, tellurium, aluminum, gallium and indium ormixtures thereof. The three substituent groups are each independentlyselected from alkyls, alkenyls, halogen, substituted alkyls, aryls,arylhalides, alkoxy and halides. Preferably, the three groups areindependently selected from halogen, mono or multicyclic (includinghalosubstituted) aryls, alkyls, and alkenyl compounds and mixturesthereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkylgroups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbonatoms and aryl groups having 3 to 20 carbon atoms (including substitutedaryls). More preferably, the three groups are alkyls having 1 to 4carbon groups, phenyl, naphthyl or mixtures thereof. Even morepreferably, the three groups are halogenated, preferably fluorinated,aryl groups. Most preferably, the neutral stoichiometric activator istrisperfluorophenyl boron or trisperfluoronaphthyl boron.

[0171] Ionic stoichiometric activator compounds may contain an activeproton, or some other cation associated with, but not coordinated to, oronly loosely coordinated to, the remaining ion of the ionizing compound.Such compounds and the like are described in European publicationsEP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401,5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

[0172] Preferred activators include a cation and an anion component, andmay be represented by the following formula:

(W^(f+))_(g)(NCA^(h−)) _(i)

[0173] W^(f+) is a cation component having the charge f+

[0174] NCA^(h−) is a non-coordinating anion having the charge h−

[0175] f is an integer from 1 to 3.

[0176] h is an integer from 1 to 3.

[0177] g and h are constrained by the relationship: (g)×(f)=(h)×(i).

[0178] The cation component, (W^(f+)) may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an akyl or aryl, from ananalogous metallocene or Group 15 containing transition metal catalystprecursor, resulting in a cationic transition metal species.

[0179] In a preferred embodiment, the activators include a cation and ananion component, and may be represented by the following formula:

(LB−H^(f+))_(g)(NCA^(h−))_(i)

[0180] wherein

[0181] LB is a neutral Lewis base;

[0182] H is hydrogen;

[0183] NCA^(h−) is a non-coordinating anion having the charge h−

[0184] f is an integer from 1 to 3,

[0185] h is an integer from 1 to 3,

[0186] g and h are constrained by the relationship: (g)×(f)=(h)×(i).

[0187] The activating cation (W^(f+)) may be a Bronsted acid,(LB−H^(f+)), capable of donating a proton to the transition metalcatalytic precursor resulting in a transition metal cation, includingammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof,preferably ammoniums of methylamine, aniline, dimethylamine,diethylamine, N-methylaniline, diphenylamine, trimethylamine,triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniumsfrom triethylphosphine, triphenylphosphine, and diphenylphosphine,oxoniums from ethers such as dimethyl ether diethyl ether,tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethylthioethers and tetrahydrothiophene and mixtures thereof.

[0188] The activating cation (W^(f+)) may also be an abstracting moietysuch as silver, carboniums, tropylium, carbeniums, ferroceniums andmixtures, preferably carboniums and ferroceniums. Most preferably(W^(f+)) is triphenyl carbonium or N,N-dimethylanilinium.

[0189] The anion component (NCA^(h−)) includes those having the formula[T^(J+)Qk]^(h−) wherein j is an integer from 1 to 3; k is an integerfrom 2 to 6; k−j=h; T is an element selected from Group 13 or 15 of thePeriodic Table of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable (NCA^(h−)) also include diboroncompounds as disclosed in U.S. Pat. No. 5,447,895, which is fullyincorporated herein by reference.

[0190] Additional suitable anions are known in the art and will besuitable for use with the catalysts of the invention. See in particular,U.S. Pat. No. 5,278,119 and the review articles by S. H. Strauss, “TheSearch for Larger and More Weakly Coordinating Anions”, Chem. Rev., 93,927-942 (1993) and C. A. Reed, “Carboranes: A New Class of WeaklyCoordinating Anions for Strong Electrophiles, Oxidants and Superacids”,Acc. Chem. Res., 31, 133-139 (1998).

[0191] Illustrative, but not limiting examples of boron compounds whichmay be used as an activating cocatalyst in the preparation of theimproved catalysts of this invention are tri-substituted ammonium saltssuch as:

[0192] trimethylammonium tetraphenylborate,

[0193] triethylammonium tetraphenylborate,

[0194] tripropylammonium tetraphenylborate,

[0195] tri(n-butyl)ammonium tetraphenylborate,

[0196] tri(t-butyl)ammonium tetraphenylborate,

[0197] N,N-dimethylanilinium tetraphenylborate,

[0198] N,N-diethylanilinium tetraphenylborate,

[0199] N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,

[0200] trimethylammonium tetrakis(pentafluorophenyl)borate,

[0201] triethylammonium tetrakis(pentafluorophenyl)borate,

[0202] tripropylammonium tetrakis(pentafluorophenyl)borate,

[0203] tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0204] tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0205] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0206] N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

[0207]N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

[0208] trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,

[0209] triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

[0210] tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

[0211] tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,

[0212] dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,

[0213] N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

[0214] N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,and

[0215]N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;

[0216] dialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and tri-substituted phosphonium saltssuch as: triphenylphosphonium tetrakis(pentafluorophenyl)borate,tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

[0217] Most preferably, the ionic stoichiometric activator isN,N-dimethylanilinium tetra(perfluorophenyl)borate and/ortriphenylcarbenium tetra(perfluorophenyl)borate.

[0218] In one embodiment, activation methods using ionizing ioniccompounds not containing an active proton but capable of producing ananalogous metallocene catalyst cation and their non-coordinating anionare also contemplated and are described in EP-A-0 426 637, EP-A-0 573403 and U.S. Pat. No. 5,387,568, which are all herein incorporated byreference.

[0219] The term “non-coordinating anion” (NCA) means an anion whicheither does not coordinate to said cation or which is only weaklycoordinated to said cation thereby remaining sufficiently labile to bedisplaced by a neutral Lewis base. “Compatible” non-coordinating anionsare those which are not degraded to neutrality when the initially formedcomplex decomposes. Non-coordinating anions useful in accordance withthis invention are those that are compatible, stabilize the metal cationin the sense of balancing its ionic charge, yet retain sufficientliability to permit displacement by an ethylenically or acetylenicallyunsaturated monomer during polymerization. These types of cocatalystssometimes use tri-isobutyl aluminum or tri-octyl aluminum as ascavenger.

[0220] Invention process also can employ cocatalyst compounds oractivator compounds that are initially neutral Lewis acids but form acationic metal complex and a noncoordinating anion, or a zwitterioniccomplex upon reaction with the invention compounds. For example,tris(pentafluorophenyl)boron or aluminum act to abstract a hydrocarbylor hydride ligand to yield an invention cationic metal complex andstabilizing noncoordinating anion, see EP-A-0 427 697 and EP-A-0 520 732for illustrations of analogous Group-4 metallocene compounds. Also, seethe methods and compounds of EP-A-0 495 375. For formation ofzwitterionic complexes using analogous Group 4 compounds, see U.S. Pat.Nos. 5,624,878; 5,486,632; and 5,527,929.

[0221] Additional neutral Lewis-acids are known in the art and aresuitable for abstracting formal anionic ligands. See in particular thereview article by E. Y. -X. Chen and T. J. Marks, “Cocatalysts forMetal-Catalyzed Olefin Polymerization: Activators, Activation Processes,and Structure-Activity Relationships”, Chem. Rev. 2000, 100, 1391.

[0222] When the E-phenoxide complex does not contain at least onehydride or hydrocarbyl ligand but does contain at least one functionalgroup ligand, such as chloride, amido or alkoxy ligands, and thefunctional group ligands are not capable of discrete ionizingabstraction with the ionizing, anion pre-cursor compounds, thesefunctional group ligands can be converted via known alkylation reactionswith organometallic compounds such as lithium or aluminum hydrides oralkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944,EP-A1-0 570 982 and EP-A1-0 612 768 for analogous processes describingthe reaction of alkyl aluminum compounds with analogous dihalidesubstituted metallocene compounds prior to or with the addition ofactivating noncoordinating anion precursor compounds.

[0223] When the cations of noncoordinating anion precursors are Bronstedacids such as protons or protonated Lewis bases (excluding water), orreducible Lewis acids such as ferrocenium or silver cations, or alkalior alkaline earth metal cations such as those of sodium, magnesium orlithium, the catalyst-precursor-to-activator molar ratio may be anyratio. Combinations of the described activator compounds may also beused for activation. For example, tris(perfluorophenyl)boron can be usedwith methylalumoxane.

[0224] C. Non-Ionizing Activators

[0225] Activators are typically strong Lewis-acids which may play eitherthe role of ionizing or non-ionizing activator. Activators previouslydescribed as ionizing activators may also be used as non-ionizingactivators.

[0226] Abstraction of formal neutral ligands may be achieved with Lewisacids that display an affinity for the formal neutral ligands. TheseLewis acids are typically unsaturated or weakly coordinated. Examples ofnon-ionizing activators include R¹⁰(R¹¹)₃, where R¹⁰ is a group 13element and R¹¹ is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl,or a functional group. Typically, R¹¹ is an arene or a perfluorinatedarene. Non-ionizing activators also include weakly coordinatedtransition metal compounds such as low valent olefin complexes.

[0227] Non-limiting examples of non-ionizing activators include BMe₃,BEt₃, B(iBu)₃, BPh₃, B(C₆F₅)₃, AlMe₃, AlEt₃, Al(iBu)₃, AlPh₃, B(C₆F₅)₃,alumoxane, CuCl, Ni(1,5-cyclooctadiene)₂.

[0228] Additional neutral Lewis-acids are known in the art and will besuitable for abstracting formal neutral ligands. See in particular thereview article by E. Y. -X. Chen and T. J. Marks, “Cocatalysts forMetal-Catalyzed Olefin Polymerization: Activators, Activation Processes,and Structure-Activity Relationships”, Chem. Rev. 2000, 100, 1391.

[0229] Preferred non-ionizing activators include R¹⁰(R¹¹)₃, where R¹⁰ isa group 13 element and R¹¹ is a hydrogen, a hydrocarbyl, a substitutedhydrocarbyl, or a functional group. Typically, R¹¹ is an arene or aperfluorinated arene.

[0230] More preferred non-ionizing activators include B(R¹²)₃, where R¹²is a an arene or a perfluorinated arene. Even more preferrednon-ionizing activators include B(C₆H₅)₃ and B(C₆F₅)₃. A particularlypreferred non-ionizing activator is B(C₆F₅)₃. More preferred activatorsare ionizing and non-ionizing activators based on perfluoroaryl boraneand perfluoroaryl borates such as PhNMe₂ ^(H+) B(C₆F₅)₄ ⁻, (C₆H₅)₃C⁺B(C₆F₅)₄ ⁻, and B(C₆F₅)₃.

[0231] It appears that alumoxane and aluminum alkyl activators may actto reduce molecular weight. While not wishing to be bound by theory, webelieve however, that in some embodiments the alumoxane or aluminumalkyl may not affect molecular weight or may even increase it.

[0232] In general the combined metal compounds and the activator arecombined in ratios of about 1000:1 to about 0.5:1. In a preferredembodiment the metal compounds and the activator are combined in a ratioof about 300:1 to about 1:1, preferably about 150:1 to about 1:1, forboranes, borates, aluminates, etc. the ratio is preferably about 1:1 toabout 10:1 and for alkyl aluminum compounds (such as diethylaluminumchloride combined with water) the ratio is preferably about 0.5:1 toabout 10:1.

[0233] In a preferred embodiment the ratio of the first catalyst to thesecond or additional catalyst is 5:95 to 95:5, preferably 25:75 to75:25, even more preferably 40:60 to 60:40.

[0234] In another embodiment the catalyst compositions of this inventioninclude a support material or carrier. For example, the one or morecatalyst components and/or one or more activators may be deposited on,contacted with, vaporized with, bonded to, or incorporated within,adsorbed or absorbed in, or on, one or more supports or carriers.

[0235] The support material is any of the conventional supportmaterials. Preferably the supported material is a porous supportmaterial, for example, talc, inorganic oxides and inorganic chlorides.Other support materials include resinous support materials such aspolystyrene, functionalized or crosslinked organic supports, such aspolystyrene divinyl benzene polyolefins or polymeric compounds,zeolites, clays, or any other organic or inorganic support material andthe like, or mixtures thereof.

[0236] The preferred support materials are inorganic oxides that includethose Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supportsinclude silica, which may or may not be dehydrated, fumed silica,alumina (WO 99/60033), silica-alumina and mixtures thereof. Other usefulsupports include magnesia, titania, zirconia, magnesium chloride (U.S.Pat. No. 5,965,477), montmorillonite (European Patent EP-B1 0 511 665),phyllosilicate, zeolites, talc, clays (U.S. Pat. No. 6,034,187) and thelike. Also, combinations of these support materials may be used, forexample, silica-chromium, silica-alumina, silica-titania and the like.Additional support materials may include those porous acrylic polymersdescribed in EP 0 767 184 B1, which is incorporated herein by reference.Other support materials include nanocomposites as described in PCT WO99/47598, aerogels as described in WO 99/48605, spherulites as describedin U.S. Pat. No. 5,972,510 and polymeric beads as described in WO99/50311, which are all herein incorporated by reference.

[0237] It is preferred that the support material, most preferably aninorganic oxide, has a surface area in the range of from about 10 toabout 700 m²/g, pore volume in the range of from about 0.1 to about 4.0cc/g and average particle size in the range of from about 5 to about 500μm. More preferably, the surface area of the support material is in therange of from about 50 to about 500 m²/g, pore volume of from about 0.5to about 3.5 cc/g and average particle size of from about 10 to about200 μm. Most preferably the surface area of the support material is inthe range is from about 100 to about 400 m²/g, pore volume from about0.8 to about 3.0 cc/g and average particle size is from about 5 to about100 μm. The average pore size of the carrier of the invention typicallyhas pore size in the range of from 10 to 1000 Å, preferably 50 to about500 Å, and most preferably 75 to about 350 Å.

[0238] Monomers

[0239] For purposes of this invention and the claims thereto the termunsaturated monomer includes olefins, polar monomers, dienes, cyclics,and the like.

[0240] In a preferred embodiment the catalyst compounds of thisinvention are used to polymerize at least one olefin monomer and atleast one polar monomer. For purposes of this invention and the claimsthereto, an olefin monomer is defined to be a monomer comprising onlycarbon and hydrogen having at least one unsaturation, and a polarmonomer is defined to be a monomer comprising carbon, hydrogen and atleast one heteroatom, and having at least one unsaturation. Preferredolefin monomers include C₂ to C₁₀₀ olefins, preferably C₂ to C₆₀olefins, preferably C₂ to C₄₀ olefins, preferably C₂ to C₂₀ olefins,preferably C₂ to C₁₂ olefins. In some embodiments, preferred olefinmonomers include linear, branched or cyclic alpha-olefins, preferably C₂to C₁₀₀ alpha-olefins, preferably C₂ to C₆₀ alpha-olefins, preferably C₂to C₄₀ alpha-olefins, preferably C₂ to C₂₀ alpha-olefins, preferably C₂to C₁₂ alpha-olefins. Preferred olefin monomers may be one or more ofethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl-hexene-1, and 5-ethyl-1-nonene.

[0241] Preferred olefin monomers may also includearomatic-group-containing monomers containing up to 30 carbon atoms.Suitable aromatic-group-containing monomers comprise at least onearomatic structure, preferably from one to three, more preferably aphenyl, indenyl, fluorenyl, or naphthyl moiety. Thearomatic-group-containing monomer further comprises at least onepolymerizable double bond such that after polymerization, the aromaticstructure will be pendant from the polymer backbone. The aromatic-groupcontaining monomer may further be substituted with one or morehydrocarbyl groups including but not limited to C₁ to C₁₀ alkyl groups.Additionally two adjacent substitutions may be joined to form a ringstructure. Preferred aromatic-group-containing monomers contain at leastone aromatic structure appended to a polymerizable olefinic moiety.Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,para-methylstyrene, 4-phenyl-1-butene, and allyl benzene.

[0242] Non aromatic cyclic group containing monomers are also preferredfor use as olefin monomers. These monomers can contain up to 30 carbonatoms. Suitable non-aromatic cyclic group containing monomers preferablyhave at least one polymerizable olefinic group that is either pendant onthe cyclic structure or is part of the cyclic structure. The cyclicstructure may also be further substituted by one or more hydrocarbylgroups such as, but not limited to, C₁ to C₁₀ alkyl groups. Preferrednon-aromatic cyclic group containing monomers include vinylcyclohexane,vinylcyclopentane, cyclopentene, cyclohexene, cyclobutene,vinyladamantane and the like.

[0243] Preferred diolefin (also referred to as diene) monomers useful inthis invention as olefin monomers include any hydrocarbon structure,preferably C₄ to C₃₀, having at least two unsaturated bonds, wherein atleast one, typically two, of the unsaturated bonds are readilyincorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,cyclohexadiene, vinylnorbornene, norbornadiene, ethylidene norbornene,divinylbenzene, dicyclopentadiene, or higher ring containing diolefinswith or without substituents at various ring positions. Alternately, thediolefin monomer may be selected from linear or branched aliphaticdienes having a non-di-vinyl structure. These diolefins have a structurein which one olefin is a vinyl group and the remaining olefin is aninternal 1,2-disubstituted, trisubstituted, or tetrasubstituted olefin.Preferred non-di-vinyl diolefins include 7-methyl-1,6-octadiene,1,4-hexadiene, and 4-vinyl-1-cyclohexene.

[0244] Preferred polar monomers for use in this invention includemonomers containing a group 13, 14 (other than carbon), 15, 16, or 17heteroatom; preferably monomers containing one or more of aluminum,boron, silicon, nitrogen, oxygen, sulfur, phosphorus, bromine, chlorine,iodine, fluorine, and the like. It is particularly preferred that theheteroatom(s) is nitrogen and or oxygen. The heteroatom may be attacheddirectly to the double bond of the olefin monomer or cyclic monomer, oralternately may be attached to any other carbon atom(s). If desired, theheteroatom may comprise part of a ring structure. Preferred polarmonomers include monomers containing one or more heteroatom containinggroups, which are selected from the group consisting of: siloxy, silane,alcohol (hydroxy), dihydroxy, phenol, acetal, epoxide, carbonate, methylether, ethyl ether, propyl ether, butyl ether, isobutyl ether, sec-butylether, tert-butyl ether, cyclohexyl ether, phenyl ether, benzyl ether,carboxylic acid, carboxylic salt, carboxylic anhydride, methyl ester,ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester,sec-butyl ester, tert-butyl ester, cyclohexyl ester, phenyl ester,benzyl ester, acetate, nitrile, imine, trimethylsilyl ether,di-tert-butylmethylsilyl ether, trimethylsilane and other alkyl silanes,borane, alkyl boranes, aryl boranes, alanes, aluminates, carboxylic acidtrimethylsilyl ether, carboxylic acid di-tert-butylmethylsilyl ether,sulfonate, nitro, amine, amide, aldehyde, ketone, thiol, and sulfide. Insome embodiments, it is preferred that the heteroatom containing groupbe selected from the group consisting of hydroxy, dihydroxy, acetal,trimethylsilyl ether, acetate, methyl ester, ethyl ester, and carbonate.In another embodiment the polar monomer comprises carbon monoxide.

[0245] In a preferred embodiment, the polar monomers may be selectedfrom linear alpha-vinyl, omega-polar monomers in which the heteroatomcontaining group(s) are attached to the carbon termini most distant fromthe vinyl unit (or also to the next most distant carbon, for the case ofmultiple heteroatom containing groups). More preferably, the linearalpha-vinyl, omega-polar monomers contain from 2 to 30 carbon atoms,with 0 to 28 carbon atoms separating the vinyl and heteroatom. Mostpreferably, the linear alpha-vinyl, omega-polar monomers contain from 2to 18 carbon atoms, with 0 to 11 carbon atoms separating the vinyl andheteroatoms. In some cases, the linear alpha-vinyl, omega-polar monomermay include a cyclic group as part of the heteroatom containing group,wherein the cyclic group does not contain the polymerizing olefin orserve to separate the vinyl and polar groups. Preferred linearalpha-vinyl, omega-polar monomers include: 3-buten-1-ol,2-methyl-3-buten-1-ol, 3-butene-1,2-diol, 4-penten-1-ol,4-pentene-1,2-diol, 5-hexen-1-ol, 5-hexene-1,2-diol, 6-hepten-1-ol,6-heptene-1,2-diol, 7-octen-1-ol, 7-octene-1,2-diol, 8-nonen-1-ol,8-nonene-1,2-diol, 9-decen-1-ol, 9-decene-1,2-diol, 10-undecen-1-ol,10-undecene-1,2-diol, 11-dodecen-1-ol, 11-dodecene-1,2-diol,12-tridecen-1-ol, 12-tridecene-1,2-diol,4-(3-butenyl)-2,2-dimethyldioxolane, 1,2-epoxy-3-butene (butadienemonoxide), 2-methyl-2-vinyloxirane, 1,2-epoxy-4-pentene,1,2-epoxy-5-hexene, 1,2-epoxy-6-heptene, 1,2-epoxy-7-octene,1,2-epoxy-8-nonene, 1,2-epoxy-9-decene, 1,2-epoxy-10-undecene,1,2-epoxy-11-dodecene, 1,2-epoxy-12-tridecene, 3-buten-1-ol methylether, 4-penten-1-ol methyl ether, 5-hexen-1-ol methyl ether,6-hepten-1-ol methyl ether, 7-octen-1-ol methyl ether, 8-nonen-1-olmethyl ether, 9-decen-1-ol methyl ether, 10-undecen-1-ol methyl ether,11-dodecen-1-ol methyl ether, 12-tridecen-1-ol methyl ether, 4-pentenoicacid, 2,2-dimethyl-4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid,trans-2,4-pentadienoic acid, 2,6-heptadienoic acid, 7-octenoic acid,8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoicacid, 12-tridecenoic acid, methyl 4-pentenoate, methyl 5-hexenoate,methyl 6-heptenoate, methyl 7-octenoate, methyl 8-nonenoate, methyl9-decenoate, methyl 10-undecenoate, ethyl 10-undecenoate, methyl11-dodecenoate, methyl 12-tridecenoate, 3-butenyl acetate, pentenylacetate, hexenyl acetate, heptenyl acetate, octenyl acetate, nonenylacetate, decenyl acetate, undecenyl acetate, dodecenyl acetate,tridecenyl acetate, 4-pentene-1-nitrile, 5-hexene-1-nitrile,6-heptene-1-nitrile, 7-octene-1-nitrile, 8-nonene-1-nitrile,9-decene-1-nitrile, 10-undecene-1-nitrile, 11-dodecene-1-nitrile,12-tridecene-1-nitrile, 3-buten-1-ol trimethylsilyl ether, 4-penten-1-oltrimethylsilyl ether, 5-hexen-1-ol trimethylsilyl ether, 6-hepten-1-oltrimethylsilyl ether, 7-octen-1-ol trimethylsilyl ether, 8-nonen-1-oltrimethylsilyl ether, 9-decen-1-ol trimethylsilyl ether, 10-undecen-1-oltrimethylsilyl ether, 11-dodecen-1-ol trimethylsilyl ether,12-tridecen-1-ol trimethylsilyl ether, 2,2-dimethyl-4-pentenal,undecylenic aldehyde, 2,4-dimethyl-2,6-heptadienal, 5-hexen-2-one, andnonafluoro-1-hexene. In a preferred embodiment, the linear alpha-vinyl,omega-polar monomers are selected from the group consisting of:7-octen-1-ol, 7-octen-1-ol trimethylsilyl ether, and octenyl acetate.

[0246] Alternately, the polar monomers be selected from cyclic polarmonomers, in which the heteroatom(s) or heteroatom containing group areattached to a carbon forming part of the ring structure which eithercontains the polymerizing olefin or separates the vinyl and heteroatomgroups. Preferred cyclic polar monomers include:5-norbornene-2-carbonitrile, 5-norbornene-2-carboxaldehyde,5-norbornene-2-carboxylic acid, cis-5-norbornene-endo-2,3-dicarboxylicacid, cis-5-norbornene-2-endo-3-exo-dicarboxylic acid,5-norbornene-2-carboxylic acid methyl ester,cis-5-norbornene-endo-2,3-dicarboxylic anhydride,cis-5-norbornene-exo-2,3-dicarboxylic anhydride,5-norbornene-2-endo-3-endo-dimethanol,5-norbornene-2-endo-3-exo-dimethanol,5-norbornene-2-exo-3-exo-dimethanol, 5-norbornene-2,2,-dimethanol,5-norbornene-2-methanol, 5-norbornen-2-ol, 5-norbornen-2-oltrimethylsilyl ether, 5-norbornen-2-ol methyl ether, 5-norbornen-2-ylacetate,1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane,2-benzoyl-5-norbornene, tricyclo[4.2.1.0^(0,0)]non-7-ene-3-carboxylicacid tert-butyl ester, tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxylicacid tert-butyl ester,tricyclo[4.2.1.0^(0,0)°]non-7-ene-3,4-dicarboxylic acid anhydride,N-butyl-tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxyimide,2-cyclopenten-1-one ethylene ketal, and vinylene carbonate. In anotherpreferred embodiment, the cyclic polar monomers are selected from thegroup consisting of 5-norbornen-2-yl acetate, 5-norbornen-2-ol, and5-norbornen-2-ol trimethylsilyl ether.

[0247] In a preferred embodiment the polar monomer is selected from thegroup consisting of carbon monoxide, 3-buten-1-ol,2-methyl-3-buten-1-ol, 3-butene-1,2-diol, 4-penten-1-ol,4-pentene-1,2-diol, 5-hexen-1-ol, 5-hexene-1,2-diol, 6-hepten-1-ol,6-heptene-1,2-diol, 7-octen-1-ol, 7-octene-1,2-diol, 8-nonen-1-ol,8-nonene-1,2-diol, 9-decen-1-ol, 9-decene-1,2-diol, 10-undecen-1-ol,10-undecene-1,2-diol, 11-dodecen-1-ol, 11-dodecene-1,2-diol,12-tridecen-1-ol, 12-tridecene-1,2-diol,4-(3-butenyl)-2,2-dimethyldioxolane, 1,2-epoxy-3-butene (butadienemonoxide), 2-methyl-2-vinyloxirane, 1,2-epoxy-4-pentene,1,2-epoxy-5-hexene, 1,2-epoxy-6-heptene, 1,2-epoxy-7-octene,1,2-epoxy-8-nonene, 1,2-epoxy-9-decene, 1,2-epoxy-10-undecene,1,2-epoxy-11-dodecene, 1,2-epoxy-12-tridecene, 3-buten-1-ol methylether, 4-penten-1-ol methyl ether, 5-hexen-1-ol methyl ether,6-hepten-1-ol methyl ether, 7-octen-1-ol methyl ether, 8-nonen-1-olmethyl ether, 9-decen-1-ol methyl ether, 10-undecen-1-ol methyl ether,11-dodecen-1-ol methyl ether, 12-tridecen-1-ol methyl ether, 4-pentenoicacid, 2,2-dimethyl-4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid,trans-2,4-pentadienoic acid, 2,6-heptadienoic acid, 7-octenoic acid,8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoicacid, 12-tridecenoic acid, methyl 4-pentenoate, methyl 5-hexenoate,methyl 6-heptenoate, methyl 7-octenoate, methyl 8-nonenoate, methyl9-decenoate, methyl 10-undecenoate, ethyl 10-undecenoate, methyl11-dodecenoate, methyl 12-tridecenoate, 3-butenyl acetate, pentenylacetate, hexenyl acetate, heptenyl acetate, octenyl acetate, nonenylacetate, decenyl acetate, undecenyl acetate, dodecenyl acetate,tridecenyl acetate, 4-pentene-1-nitrile, 5-hexene-1-nitrile,6-heptene-1-nitrile, 7-octene-1-nitrile, 8-nonene-1-nitrile,9-decene-1-nitrile, 10-undecene-1-nitrile, 11-dodecene-1-nitrile,12-tridecene-1-nitrile, 3-buten-1-ol trimethylsilyl ether, 4-penten-1-oltrimethylsilyl ether, 5-hexen-1-ol trimethylsilyl ether, 6-hepten-1-oltrimethylsilyl ether, 7-octen-1-ol trimethylsilyl ether, 8-nonen-1-oltrimethylsilyl ether, 9-decen-1-ol trimethylsilyl ether, 10-undecen-1-oltrimethylsilyl ether, 11-dodecen-1-ol trimethylsilyl ether,12-tridecen-1-ol trimethylsilyl ether, 2,2-dimethyl-4-pentenal,undecylenic aldehyde, 2,4-dimethyl-2,6-heptadienal, 5-hexen-2-one,nonafluoro-1-hexene, 5-norbornene-2-carbonitrile,5-norbornene-2-carboxaldehyde, 5-norbornene-2-carboxylic acid,cis-5-norbornene-endo-2,3-dicarboxylic acid,cis-5-norbornene-2-endo-3-exo-dicarboxylic acid,5-norbornene-2-carboxylic acid methyl ester,cis-5-norbornene-endo-2,3-dicarboxylic anhydride,cis-5-norbornene-exo-2,3-dicarboxylic anhydride,5-norbornene-2-endo-3-endo-dimethanol,5-norbornene-2-endo-3-exo-dimethanol,5-norbornene-2-exo-3-exo-dimethanol, 5-norbornene-2,2,-dimethanol,5-norbornene-2-methanol, 5-norbornen-2-ol, 5-norbornen-2-oltrimethylsilyl ether, 5-norbornen-2-ol methyl ether, 5-norbornen-2-ylacetate,1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane,2-benzoyl-5-norbornene, tricyclo[4.2.1.0^(0,0)]non-7-ene-3-carboxylicacid tert-butyl ester, tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxylicacid tert-butyl ester, tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxylicacid anhydride,N-butyl-tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxyimide,2-cyclopenten-1-one ethylene ketal, and vinylene carbonate.

[0248] In a preferred embodiment, the olefin monomers are present in thepolymer at 50 mole % to 99.9 mole %, more preferably 70 to 98 mole %,more preferably 80 to 95 mole %. In a preferred embodiment, the polarmonomers are present in the polymer at 0.1 mole % to 50 mole %, basedupon the moles of all monomers present, more preferably 2 to 30 mole %,more preferably 5 to 20 mole %. In another preferred embodiment thepolar monomer is present in the polymer at 0.2 to 15 mole % and theolefin monomer(s) is present at 99.8 to 85 mole %.

[0249] In a preferred embodiment, the polar monomers are present in thefeed to the reactor at 0.1 mole % to 50 mole %, based on all monomerspresent in the feed, more preferably 2 to 30 mole %, more preferably 5to 20 mole %. In a preferred embodiment, the olefin monomers are presentin the feed to the reactor at 50 mole % to 99.9 mole %, more preferably70 to 98 mole %, more preferably 80 to 95 mole %. In another preferredembodiment the polar monomer is present in the feed to the reactor at0.2 to 15 mole % and the olefin monomer(s) is present at 99.8 to 85 mole%.

[0250] Preferred combinations of monomers include ethylene and one ormore of: 7-octen-1-ol, 7-octen-1-ol trimethylsilyl ether, octenylacetate, 5-norbornen-2-yl acetate, 5-norbornen-2-ol, and5-norbornen-2-ol trimethylsilyl ether.

[0251] Preferred combinations of monomers include propylene and one ormore of: 7-octen-1-ol, 7-octen-1-ol trimethylsilyl ether, octenylacetate, 5-norbornen-2-yl acetate, 5-norbornen-2-ol, and5-norbornen-2-ol trimethylsilyl ether.

[0252] For purposes of this disclosure, the term oligomer refers tocompositions having 2-40 mer units and the term polymer refers tocompositions having 41 or more mer units. A mer is defined as a unit ofan oligomer or polymer that originally corresponded to the monomer(s)used in the oligomerization or polymerization reaction. For example, themer of polyethylene would be ethylene. Oligomers and polymers may haveone kind of mer unit or may have many different mer units. For exampleone may have an oligomer of ethylene alone or an oligomer of butene,ethylene and propylene.

[0253] In an embodiment herein, the process described herein is used toproduce an oligomer of any of the olefin and polar monomers listedabove. Preferred olefin monomers for use in oligomers include any C₂ toC₂₀ olefins, preferably C₂ to C₁₂ alpha-olefins, most preferablyethylene, propylene and or butene. Preferred polar monomers for use inoligomers include 7-octen-1-ol, 7-octen-1-ol trimethylsilyl ether,octenyl acetate, 5-norbornen-2-yl acetate, 5-norbornen-2-ol, and5-norbornen-2-ol trimethylsilyl ether.

[0254] In a preferred embodiment the process described herein may beused to produce homopolymers or copolymers. (For the purposes of thisinvention and the claims thereto a copolymer may comprise two, three,four or more different monomer units.) Preferred polymers producedherein include copolymers of any of the above olefin monomers with anyof the above polar monomers. In a preferred embodiment the processdescribed herein may be used to produce a copolymer comprising ethyleneand one or more of the polar monomers listed above. In anotherembodiment the process described herein may be used to produce acopolymer comprising propylene and one or more of the polar monomerslisted above. In another embodiment the process described herein may beused to produce a copolymer comprising ethylene, propylene, and one ormore of the polar monomers listed above.

[0255] In another preferred embodiment the polymer produced herein is acopolymer of ethylene and one or more polar monomers, preferably one ormore linear alpha-vinyl, omega-polar monomers or cyclic polar monomers.Most preferably the polymer produced herein is a copolymer of ethyleneand one or more of 7-octen-1-ol, 7-octen-1-ol trimethylsilyl ether,octenyl acetate, 5-norbornen-2-yl acetate, 5-norbornen-2-ol, and5-norbornen-2-ol trimethylsilyl ether.

[0256] In another preferred embodiment the polymer produced herein is acopolymer of propylene and one or more polar monomers, preferably one ormore linear alpha-vinyl, omega-polar monomers or cyclic polar monomers.Most preferably the polymer produced herein is a copolymer of propyleneand one or more of 7-octen-1-ol, 7-octen-1-ol trimethylsilyl ether,octenyl acetate, 5-norbornen-2-yl acetate, 5-norbornen-2-ol, and5-norbornen-2-ol trimethylsilyl ether.

[0257] In another preferred embodiment the polymer produced herein is aterpolymer of ethylene, propylene, and one or more polar monomers,preferably one or more linear alpha-vinyl, omega-polar monomers orcyclic polar monomers. Most preferably the polymer produced herein is aterpolymer of ethylene, propylene and one or more of 7-octen-1-ol,7-octen-1-ol trimethylsilyl ether, octenyl acetate, 5-norbornen-2-ylacetate, 5-norbornen-2-ol, and 5-norbornen-2-ol trimethylsilyl ether.

[0258] In a preferred embodiment the polymers described herein furthercomprise one or more dienes at up to 10 weight %, preferably at 0.00001to 1.0 weight %, preferably 0.002 to 0.5 weight %, even more preferably0.003 to 0.2 weight %, based upon the total weight of the composition.In some embodiments 500 ppm or less of diene is added to thepolymerization, preferably 400 ppm or less, preferably or 300 ppm orless. In other embodiments at least 50 ppm of diene is added to thepolymerization, or 100 ppm or more, or 150 ppm or more. Preferred dienesinclude butadiene, pentadiene, hexadiene, heptadiene, octadiene,nonadiene, decadiene, undecadiene, dodecadiene, and cyclopentadiene.

[0259] In a preferred embodiment the polar monomer comprises one or moreof any alpha-vinyl, omega-polar monomers or cyclic polar monomers,including 7-octen-1-ol, 7-octen-1-ol trimethylsilyl ether, octenylacetate, 5-norbornen-2-yl acetate, 5-norbornen-2-ol, and5-norbornen-2-ol trimethylsilyl ether.

[0260] In another embodiment, the polymer produced herein comprises:

[0261] a first olefin monomer present at from 40 to 95 mole %,preferably 50 to 90 mole %, more preferably 60 to 80 mole %, and

[0262] a second olefin monomer present at from 5 to 60 mole %,preferably 10 to 40 mole %, more preferably 20 to 40 mole %,

[0263] a third olefin monomer present at from 0 to 10 mole %, morepreferably from 0.5 to 5 mole %, more preferably 1 to 3 mole %,

[0264] a polar monomer present at from 0.001 to 50 mole %, preferablyfrom 0.01 to 30 mole %, more preferably from 0.1 to 20 mole %, mostpreferably from 0.2 to 15 mole %.

[0265] In a preferred embodiment the first olefin monomer comprises oneor more of any C₃ to C₈ linear, branched or cyclic alpha-olefins,including propylene, butene (and all isomers thereof), pentene (and allisomers thereof), hexene (and all isomers thereof), heptene (and allisomers thereof), and octene (and all isomers thereof). Preferredmonomers include propylene, 1-butene, 1-hexene, 1-octene, and the like.

[0266] In a preferred embodiment the second olefin monomer comprises oneor more of any C₂ to C₄₀ linear, branched or cyclic alpha-olefins,including ethylene, propylene, butene, pentene, hexene, heptene, octene,nonene, decene, undecene, dodecene, hexadecene,3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1,5-ethyl-1-nonene,cyclooctene, cyclopentene, and cyclohexene.

[0267] In a preferred embodiment the third olefin monomer comprises oneor more of any C₂ to C₄₀ linear, branched or cyclic alpha-olefins,including3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1,5-ethyl-1-nonene,cyclooctene, cyclopentene, and cyclohexene. In a preferred embodimentthe third monomer comprises one or more dienes.

[0268] Oligomerization Processes

[0269] The catalyst compositions described above may be used tooligomerize or polymerize any unsaturated monomer, however they arepreferably used to oligomerize olefins, typically alpha-olefins, withpolar monomers. In the instant oligomerization processes, the processtemperature may be −100° C. to 300° C., −20° C. to 200° C., or 0° C. to150° C. Some embodiments select oligomerization pressures (gauge) from 0kPa-35 MPa or 500 kPa-15 MPa. In a preferred embodiment, conditions thatfavor oligomer production include using aluminum alkyls (as activator orscavenger, etc.) and/or selecting a nickel catalyst compound where Ar¹and or Ar² comprises phenyl and/or mesityl. A preferred feedstock forthe oligomerization process is the alpha-olefin, ethylene, incombination with any alpha-vinyl, omega-polar monomer or cyclic polarmonomer. But other alpha-olefins, including but not limited to propyleneand 1-butene, may also be used in place of or combined with ethylene.Preferred alpha-olefins include any C₂ to C₄₀ alpha-olefin, preferablyand C₂ to C₂₀ alpha-olefin, preferably any C₂ to C₁₂ alpha-olefin,preferably ethylene, propylene, and butene, most preferably ethylene.Preferred polar monomers include 7-octen-1-ol, 7-octen-1-oltrimethylsilyl ether, octenyl acetate, 5-norbornen-2-yl acetate,5-norbornen-2-ol, and 5-norbornen-2-ol trimethylsilyl ether. Dienes maybe used in the processes described herein, preferably alpha,omega-dienes are used alone or in combination with mono-alpha olefins.

[0270] Preferred oligomerization processes may be run in the presence ofvarious liquids, particularly aprotic organic liquids. Preferably thehomogeneous catalyst system, olefin monomers, polar monomers, andproduct are soluble in these liquids. A supported (heterogeneous)catalyst system may also be used, but will form a slurry rather than asolution. Suitable liquids for both homo- and heterogeneous catalystsystems, include alkanes, alkenes, cycloalkanes, selected halogenatedhydrocarbons, aromatic hydrocarbons, and in some cases,hydrofluorocarbons. Useful solvents specifically include hexane,toluene, cyclohexane, benzene, and mixtures of toluene and diethylether.

[0271] Polymerization Processes

[0272] Typically one or more E-phenoxide compounds, one or more optionalactivators, one or more olefin monomers and one or more polar monomersare contacted to produce polymer. The components may be contacted in asolution, bulk, gas or slurry polymerization process or a combinationthereof, preferably solution phase or bulk phase polymerization process.

[0273] In general the combined E-phenoxide compounds and the activatorare combined in ratios of about 1:10,000 to about 1:1, in otherembodiments the combined E-phenoxide compounds and the activator arecombined in ratios of 1:1 to 100:1. When alumoxane or aluminum alkylactivators are used, the combined pre-catalyst-to-activator molar ratiois from 1:5000 to 10:1, alternatively from 1:1000 to 10:1;alternatively, 1:500 to 2:1; or 1:300 to 1:1. When ionizing activatorsare used, the combined pre-catalyst-to-activator molar ratio is from10:1 to 1:10; 5:1 to 1:5; 2:1 to 1:2; or 1.2:1 to 1:1. Multipleactivators may be used, including using mixtures of alumoxanes oraluminum alkyls with ionizing activators.

[0274] One or more reactors in series or in parallel may be used in thepresent invention. Catalyst component and activator may be delivered asa solution or slurry, either separately to the reactor, activatedin-line just prior to the reactor, or preactivated and pumped as anactivated solution or slurry to the reactor. A preferred operation istwo solutions activated in-line. Polymerizations are carried out ineither single reactor operation, in which monomer, comonomers,catalyst/activator, scavenger, and optional modifiers are addedcontinuously to a single reactor or in series reactor operation, inwhich the above components are added to each of two or more reactorsconnected in series. The catalyst components can be added to the firstreactor in the series. The catalyst component may also be added to bothreactors, with one component being added to first reaction and anothercomponent to other reactors.

[0275] Gas Phase Polymerization

[0276] Generally, in a fluidized gas bed process used for producingpolymers, a gaseous stream containing one or more monomers iscontinuously cycled through a fluidized bed in the presence of acatalyst under reactive conditions. The gaseous stream is withdrawn fromthe fluidized bed and recycled back into the reactor. Simultaneously,polymer product is withdrawn from the reactor and fresh monomer is addedto replace the polymerized monomer. (See for example U.S. Pat. Nos.4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922,5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228 all of whichare fully incorporated herein by reference.)

[0277] The reactor pressure in a gas phase process may vary from about10 psig (69 kPa) to about 500 psig (3448 kPa), preferably from about 100psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range offrom about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0278] The reactor temperature in the gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 110° C.,and most preferably in the range of from about 70° C. to about 95° C. Inanother embodiment when high density polyethylene is desired then thereactor temperature is typically between 70 and 105° C.

[0279] The productivity of the catalyst or catalyst system in a gasphase system is influenced by the partial pressure of the main monomer.The preferred mole percent of the main monomer, ethylene or propylene,preferably ethylene, is from about 25 to 90 mole percent and thecomonomer partial pressure is in the range of from about 138 kPa toabout 517 kPa, preferably about 517 kPa to about 2069 kPa, which aretypical conditions in a gas phase polymerization process. Also in somesystems the presence of comonomer can increase productivity.

[0280] In a preferred embodiment, the reactor utilized in the presentinvention is capable of producing more than 500 lbs of polymer per hour(227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher, preferablygreater than 1000 lbs/hr (455 Kg/hr), more preferably greater than10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr(15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr(22,700 Kg/hr) and preferably greater than 65,000 lbs/hr (29,000 Kg/hr)to greater than 100,000 lbs/hr (45,500 Kg/hr), and most preferably over100,000 lbs/hr (45,500 Kg/hr).

[0281] Other gas phase processes contemplated by the process of theinvention include those described in U.S. Pat. Nos. 5,627,242, 5,665,818and 5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202and EP-B-634 421 all of which are herein fully incorporated byreference.

[0282] In another preferred embodiment the catalyst system in is liquidform and is introduced into the gas phase reactor into a resin particlelean zone. For information on how to introduce a liquid catalyst systeminto a fluidized bed polymerization into a particle lean zone, pleasesee U.S. Pat. No. 5,693,727, which is incorporated by reference herein.

[0283] Slurry Phase Polymerization

[0284] A slurry polymerization process generally operates between 1 toabout 50 atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068kPa) or even greater and temperatures in the range of 0° C. to about120° C. In a slurry polymerization, a suspension of solid, particulatepolymer is formed in a liquid polymerization diluent medium to whichmonomer and comonomers along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process shouldbe operated above the reaction diluent critical temperature andpressure. Preferably, a hexane or an isobutane medium is employed.

[0285] In one embodiment, a preferred polymerization technique of theinvention is referred to as a particle form polymerization, or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

[0286] In another embodiment, the slurry process is carried outcontinuously in a loop reactor. The catalyst, as a slurry in isobutaneor as a dry free flowing powder, is injected regularly to the reactorloop, which is itself filled with circulating slurry of growing polymerparticles in a diluent of isobutane containing monomer and comonomer.Hydrogen, optionally, may be added as a molecular weight control. Thereactor is maintained at a pressure of 3620 kPa to 4309 kPa and at atemperature in the range of about 60° C. to about 104° C. depending onthe desired polymer melting characteristics. Reaction heat is removedthrough the loop wall since much of the reactor is in the form of adouble-jacketed pipe. The slurry is allowed to exit the reactor atregular intervals or continuously to a heated low pressure flash vessel,rotary dryer and a nitrogen purge column in sequence for removal of theisobutane diluent and all unreacted monomer and comonomers. Theresulting hydrocarbon free powder is then compounded for use in variousapplications.

[0287] In another embodiment, the reactor used in the slurry process ofthe invention is capable of and the process of the invention isproducing greater than 2000 lbs of polymer per hour (907 Kg/hr), morepreferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferablygreater than 10,000 lbs/hr (4540 Kg/hr). In another embodiment theslurry reactor used in the process of the invention is producing greaterthan 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greaterthan 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500Kg/hr).

[0288] In another embodiment in the slurry process of the invention thetotal reactor pressure is in the range of from 400 psig (2758 kPa) to800 psig (5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig(4827 kPa), more preferably 500 psig (3448 kPa) to about 650 psig (4482kPa), most preferably from about 525 psig (3620 kPa) to 625 psig (4309kPa).

[0289] In yet another embodiment in the slurry process of the inventionthe concentration of predominant monomer in the reactor liquid medium isin the range of from about 1 to 10 weight percent, preferably from about2 to about 7 weight percent, more preferably from about 2.5 to about 6weight percent, most preferably from about 3 to about 6 weight percent.

[0290] Another process of the invention is where the process, preferablya slurry or gas phase process is operated in the absence of oressentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This process isdescribed in PCT publication WO 96/08520 and U.S. Pat. No. 5,712,352,which are herein fully incorporated by reference.

[0291] In another embodiment the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-isobutyl aluminum and anexcess of alumoxane or modified alumoxane.

[0292] Homogeneous, Bulk or Solution Phase Polymerization

[0293] The catalysts described herein can be used advantageously inhomogeneous solution processes. Generally this involves polymerizationin a continuous reactor in which the polymer formed and the startingmonomer and catalyst materials supplied, are agitated to reduce or avoidconcentration gradients. Suitable processes operate above the meltingpoint of the polymers at high pressures, from 1 to 3000 bar (10-30,000MPa), in which the monomer acts as diluent or in solution polymerizationusing a solvent.

[0294] Temperature control in the reactor is obtained by balancing theheat of polymerization and with reactor cooling by reactor jackets orcooling coils to cool the contents of the reactor, auto refrigeration,pre-chilled feeds, vaporization of liquid medium (diluent, monomers orsolvent) or combinations of all three. Adiabatic reactors withpre-chilled feeds may also be used. The reactor temperature depends onthe catalyst used. In general, the reactor temperature preferably canvary between about 0° C. and about 160° C., more preferably from about10° C. to about 140° C., and most preferably from about 40° C. to about120° C. In series operation, the second reactor temperature ispreferably higher than the first reactor temperature. In parallelreactor operation, the temperatures of the two reactors are independent.The pressure can vary from about 1 mm Hg (0.001 bar) to 2500 bar (25,000MPa), preferably from 0.1 bar to 1600 bar (1-16,000 MPa), mostpreferably from 1.0 to 500 bar (10-5000 MPa).

[0295] Each of these processes may also be employed in single reactor,parallel or series reactor configurations. The liquid processes comprisecontacting olefin monomers with the above described catalyst system in asuitable diluent or solvent and allowing said monomers to react for asufficient time to produce the desired polymers. Hydrocarbon solventsare suitable, both aliphatic and aromatic. Alkanes, such as hexane,pentane, isopentane, and octane, are preferred. Alternately, mixtures ofpolar and nonpolar solvents can be used. For purposes of this invention,a nonpolar solvent is defined as a solvent that contains only carbon andhydrogen atoms (such as an alkene or arene), while a polar solvent isdefined a solvent that contains at least one Group 15, 16, or 17heteroatom (such as oxygen, fluorine, or chlorine). Particularly, amixture of a nonpolar aliphatic or aromatic solvent with a polarsolvent, particularly diethyl ether, is preferred. Preferred polarsolvents include diethyl ether, methyl t-butyl ether, tetrahydrofuran,di-n-butyl ether, methyl propyl ether, di-n-propyl ether, diisopropylether, ethyl acetate, and acetone. Preferred non-polar solvents includetoluene, hexane, pentane, isopentane, and octane. The process can becarried out in a continuous stirred tank reactor, batch reactor or plugflow reactor, or more than one reactor operated in series or parallel.These reactors may have or may not have internal cooling and the monomerfeed my or may not be refrigerated. See the general disclosure of U.S.Pat. No. 5,001,205 for general process conditions. See also,international application WO 96/33227 and WO 97/22639 for moreinformation. In a preferred embodiment, a mixture of toluene and diethylether is used as the diluent or solvent.

[0296] Polymers Produced

[0297] The polymers produced herein may have a weight average molecularweight (Mn) 1000 to 1,000,000, preferably from 1500 to 500,000. Thepolymers produced herein may have a molecular weight distribution(Mw/Mn) of up to 6, preferably from 1.1 to 4.5, more preferably from 1.1to 3.5.

[0298] In a preferred embodiment, this invention relates to a copolymercomprising olefin monomer and from 0.2 to 30 mole %, preferably 0.2 to15 mole % of a polar monomer where the copolymer has less than 25 totalalkyl branches per 1000 carbons and the copolymer has 45% or more(alternately 50% or more, alternately 55% or more) of its olefinic endgroups as vinyls.

[0299] Any of the polymers or oligomers produced by this invention, maybe further functionalized after polymerization or oligomerization.Preferred functional groups for post-polymerization/oligomerizationfunctionalization include maleic acid and maleic anhydride. Byfunctionalized in this instance it is meant that the polymer has beencontacted with an unsaturated acid or anhydride. Preferred unsaturatedacids or anhydrides include any unsaturated organic compound containingat least one double bond and at least one carbonyl group. Representativeacids include carboxylic acids, their anhydrides, their esters, andtheir salts, both metallic and non-metallic. Preferably the organiccompound contains an ethylenic unsaturation conjugated with a carbonylgroup (—C═O). Examples include maleic, fumaric, acrylic, methacrylic,itaconic, crotonic, alpha-methyl crotonic, and cinnamic acids as well astheir anhydrides, esters and salt derivatives. Maleic anhydride isparticularly preferred. The unsaturated acid or anhydride is preferablypresent at about 0.1 weight % to about 10 weight %, preferably at about0.5 weight % to about 7 weight %, even more preferably at about 1 toabout 4 weight %, based upon the weight of the hydrocarbon resin and theunsaturated acid or anhydride.

EXAMPLES

[0300] Catalysts

[0301] The precatalyst compounds used in the following examples arerepresented by the formulae below:

Example 1

[0302] Preparation of[2-(2′,6′-Diisopropylphenylazo)-4-methyl-6-(9-anthracenyl)phenoxide]-Nickel(phenyl)(triphenylphosphine)(Catalyst 1). Catalyst 1 was prepared as described in precedingapplication U.S. Ser. No. 10/436,741 (which is incorporated by referenceherein), where it is referred to as catalyst C. This phenol was preparedfrom a theoretical yield of 3.9 mmol of diazotized2,6-diisopropylaniline (prepared as reported (Helvetica Chimica Acta1983, 66, 1737)) quenched with a phenolate solution comprised of2-(9-anthracenyl)-4-methylphenol (0.63 g), water (20 mL), NaOH (20mmol), pyridine (2 mL), and benzene (4 mL) cooled in an ice bath. Theorganic layer was collected and depleted of volatiles on a rotaryevaporator. The crude ligand,2-(2′,6′-diisopropylphenylazo)-4-methyl-6-(9-anthracenyl)phenol, waspurified by chromatography on silica gel using 10:1 hexanes/diethylether as an eluent, followed by crystallized from methanol (slowevaporation at ambient temperature). Yield was approximately 0.30 g(29%). (PPh₃)₂Ni(Ph)(Br) (560 mg, 0.76 mmol) was added to a solution ofpotassium2-(2′,6′-diisopropylphenylazo)-4-methyl-6-(9-anthracenyl)phenoxide (0.56mmol) in THF (45 mL) (prepared by addition of a slight excess of KH tothe purified2-(2′,6′-diisopropylphenylazo)-4-methyl-6-(9-anthracenyl)phenol) causinga color change to red/brown. After 2 hours, the solvent and residualvolatiles were removed and the residue was extracted with pentane (70mL) and filtered to collect the crude insoluble product, which was driedin vacuo. Residual phosphine was removed by trituration with pentaneovernight at −30° C. to give the product as the remainingpentane-insoluble dark red/brown powder. Yield was approximately 310 mg(64%). ¹H NMR (C₆D₆): 1.27 (doublet of doublets; J=7, 18 Hz; 12H); 2.08(singlet; 3H); 4.26 (septet; J=7 Hz; 2H); 6.29 (multiplet; 3H); 6.58(triplet; J=8 Hz; 6H); 6.76 (triplet; J=8 Hz; 3H); 6.87-7.19 (multiplet;16H); 7.63 (doublet; J=8 Hz; 2H); 7.81 (doublet; J=8 Hz; 2H); 7.86(singlet; 1H); 7.94 (doublet; J=2 Hz; 1H) ppm. The2-(9-anthracenyl)-4-methylphenol was prepared as follows: A 500 mL roundbottom flask was charged with 9-bromoanthracene (20.7 g, 80.5 mmol, 1.1equivalents) and (PPh₃)₂NiCl₂ (1.33 g, 2.0 mmol, 2.7% catalyst) inapproximately 150 mL THF under a nitrogen atmosphere. While stirring atambient temperature, a freshly prepared magnesium Grignard solution oftetrahydropyran(THP)-protected 2-bromo-cresol(2MgBr-CresolTHP)-(theoretical yield 75.0 mmol, 1 equivalent) in 150 mLTHF was added over a 15 minute period with little change in the solutiontemperature. The reaction was heated at reflux for 5 days, slowlycausing a change in color from brown to green. After cooling, the flaskwas moved to a fume hood and most of the solvent was evaporated vianitrogen flow. The reaction was diluted with 200 mL of hexanes, cooledin an ice bath, and any remaining Grignard or active magnesium compoundswere quenched by slow addition of 50 mL water. Recovery of the organiclayer and removal of volatiles by evaporation led to a yellow/brown oilthat deposited some light yellow powder and crystals of product uponstanding. More product was extracted from the oil by adding acetone andcollecting the white crystalline material which formed. Removal ofacetone in vacuo resulted in 7.8 g of phenol (37% yield). ¹H NMR (C₆D₆,250 MHz, 22° C.): δ 2.09 ppm, s, 3H; 4.13 ppm, s, 1H; 6.84 ppm, s, 1H;7.05-7.23 ppm, m, 6H; 7.82 ppm, d, J_(HH)=9.3 Hz, 4H; 8.24 ppm, s, 1H.

Comparative Example C1

[0303] Preparation of[2-(2′,6′-Diisopropylphenylimino)-6-(9-anthracenyl)phenoxide]-Nickel(phenyl)(triphenylphosphine)(Catalyst C1). Comparative catalyst C1 was prepared according toliterature methods (WO 98/42664) and purified by reprecipitation frombenzene into pentane (both solvents dried by distillation from sodiumbenzophenone ketyl), followed by three cycles of slurrying in diethylether (10 mL/400 mg catalyst; dried by passage through alumina) toremove soluble impurities. The resultant material containedapproximately 1.5 mol % free PPh₃ (by ³¹P NMR in CDCl₃ vs. external 85%aqueous H₃PO₄ standard, δ 31.6 ppm; C1, δ 27.74 ppm) and some residualether (by ¹H NMR).

[0304] Monomers

[0305] In the below examples, ¹³C and ¹H NMR spectra for monomers wereobtained on a Bruker Avance 400 MHz Ultrashield spectrometer or a VarianUnityPlus 500 MHz spectrometer. Spectra were referenced to CDCl₃ (¹³C,77.00 ppm; ¹H, 7.25 ppm); the following abbreviations are used:s=singlet, d=doublet, tr=triplet, q=quartet, m=multiplet. Infraredspectra were taken using a ThermoNicolet Nexus 470 FTIR running OMNICsoftware. Tandem gas chromatography/time-of-flight field ionization massspectrometry (GC-TOF-MS) was conducted using a Hewlett-Packard 6890 GCand a MicroMass GCP spectrometer. Elemental analyses were conducted byQTI Inc., Whitehouse, N.J.

[0306] Ethylene (AGT grade 4.5, 99.995%) was used as received.7-Octen-1-ol (TCI Co., 96%) was dried over 3 Å sieves for 3 days,filtered, and distilled at 50° C./2 mm (267 Pa). All other commercialcomonomers were distilled from CaH₂ at the given temperature andpressure, degassed by freeze-pump-thaw cycles, and stored at −35° C. ina freezer under argon: 1-octene (Aldrich Co., 98%, 39° C./39 mm (5200Pa)), octenyl acetate (TCI Co., 98+%, 54° C./10 mm (1333 Pa)),norbornene (Aldrich Co., 99%, 96° C./760 mm (101325 Pa)),5-norbornen-2-yl acetate (Aldrich Co., 98%, 76° C./14 mm (1867 Pa); 79:21 endo:exo by average of ¹H and ¹³C NMR). The endo:exo ratio for5-norbornen-2-yl acetate was determined by integration of the followingresonances: ¹H NMR, endo olefin (CH farthest from OAc) 6.16, exo olefin(CH farthest from OAc) 6.07, endo CHOAc 5.10, exo CHOAc 4.49 ppm; ¹³CNMR, endo olefin 138.01 and 131.15, exo olefin 140.61 and 132.24, endomethine (CH farthest from OAc) 41.82, exo methine (CH farthest from OAc)40.22 ppm.

Example 2

[0307] Synthesis of 7-octen-1-ol trimethylsily ether. In a 3-necked, 1 Lround-bottomed flask, 1-octenol (21.16 g, 165 mmol) and Et₃N (AldrichCo., used as received, 23.0 mL, 165 mmol) were dissolved in 500 mLCH₂Cl₂ under an N₂ purge. A stirbar was added and the flask was fittedwith a pressure-equalized addition funnel. In the drybox, a solution ofMe₃SiCl (Aldrich Co., used as received, 18.82 g, 173 mmol) in 100 mLCH₂Cl₂ was prepared in a round-bottomed flask sealed with a rubberseptum. This solution was cannulated into the addition funnel and addeddropwise to the stirred 1-octenol solution. White smoke and a gentlereflux were observed and a white precipitate was observed. The mixturewas stirred at room temperature overnight under N₂, cooled to 0° C., anddepleted of volatiles using a Schlenk vacuum line with an in-line trap(caution: traps containing Me₃SiCl should be vented to an inertatmosphere). The resultant solid was purged with N₂ for 0.5 hour andtaken into the drybox and extracted with 100 mL pentane. The cloudysupernatant was filtered using a glass frit and an 0.45μ Acrodisc filterto obtain a clear solution. The pentane was removed using a rotaryevaporator to give 7-octen-1-OSiMe₃ as a colorless liquid (27.71 g,83.8%) which was dried over CaH₂, distilled at 42° C./2 mm (267 Pa),degassed by freeze-pump-thaw cycles, and stored at −35° C. in a freezerunder argon. ¹H NMR (CDCl₃): δ 5.79 (d of d of tr, J_(tr)=6.7 Hz,J_(d)=10.3, 17.0 Hz, 1H, ═CH), 4.99 (d of d of tr, J_(tr)=1.7 Hz,J_(d)=1.9, 17.2 Hz, 1H, H ₂C=cis to chain), 4.91 (d of d of tr,J_(tr)=1.2 Hz, J_(d)=2.1, 10.2 Hz, 1H, H ₂C=trans to chain), 3.55 (tr,J=6.7 Hz, 2H, CH ₂OSi), 2.03 (apparent q, J=7.1 Hz, 2H), 1.51 (apparenttr, J=7.0 Hz, 2H), 1.37 (app tr, J=7.4 Hz, 2H), 1.30 (m, 4H) (CH₂), 0.09(s, 9H, SiMe₃). ¹³C NMR (CDCl₃): δ 139.06 (═CH, 1C), 114.16 (H₂ C═, 1C),62.65 (CH₂OSi), 33.64, 32.68, 28.91, 28.89, 25.68 (CH₂, each 1C), −0.49(SiMe₃, 3C). IR (NaCl thin film): 3078 (w), 2955 (sh), 2931 (vs), 2858(s), 2736 (w), 1641 (m), 1456 (w), 1438 (w), 1415 (w), 1387 (w), 1294(sh), 1259 (sh), 1251 (vs), 1099 (vs), 1031 (sh), 993 (m), 930 (sh), 910m), 873 (s), 841 (vs), 747 (m), 709 (w), 685 (w) cm⁻¹. High-resolutionGC-TOF-MS: One peak; Calculated, 200.1596; Found: 200.1588. Elementalanalysis calculated for C₁₁H₂₄OSi: C, 65.93; H, 12.07; O, 7.98; Si,14.02. Found: C, 65.56; H, 11.99.

[0308] Polymerizations

[0309] In the below examples, polymerizations were carried outsimultaneously in triplicate using three 3 oz. (70 mL) Fisher-Porterglass pressure bottles clamped side-by-side in a single large oil bath.The bottles were fitted with heads equipped with a 200 psig (1.38 MPa)pressure gauge, syringe port, vent valve, and 152 psig (1.05 MPa) safetyvalve. The bottles were fitted with screw-on cylindrical polycarbonateblast shields, in which ⅜″ diameter holes were periodically drilled toallow for efficient heating oil flow. An ethylene manifold featuringthree separate flexi-hoses attached to a single 500 cc pressure vesseltank (PVT) was used, with one regulator controlling pressure for allthree vessels.

[0310] The general polymerization procedure used was as follows: In thedrybox, a stock solution of 0.045 mmol catalyst (1 or C1) in 12 mLtoluene (dried by passage through alumina and Q-5 copper catalyst asdescribed in: Pangbom, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R.K.; Timmers, F. J. Organometallics 1996, 15, 1518) was prepared in agraduated cylinder and stirred. The solution was divided into threeseparate vials each containing exactly 4 mL. These aliquots were loadedinto three dry, air-tight 5 mL syringes which were kept in the dryboxuntil immediately before injection. Separately, 18 mmol of comonomer wasweighed out and diluted to a 24 mL volume in a 25 mL graduated cylinderand stirred. An 8 mL portion of this solution was added to each of thethree Fischer Porter tubes. Another 3 mL of toluene was added to eachtube along with a stirbar (for ethylene homopolymerization experiments,11 mL dry toluene was added to each pressure vessel along with amagnetic stirbar, rather than 3 mL toluene plus 8 mL of the toluenesolution containing the comonomer). The tubes were sealed, taken out ofthe drybox, attached to an ethylene manifold, and heated to 50° C. in anoil bath with magnetic stirring. Three pressurization cycles of thebottles to 120 psig C₂H₄ (827 kPa) followed by venting were carried outto remove residual argon. Syringe injection of the 4 mL aliquots ofactivated catalyst solution was carried out for the three bottles (finalconditions in each bottle: 0.015 mmol catalyst (1.0 mM), 6 mmolcomonomer (0.4 M), 15 mL total volume). Immediate repressurization ofthe bottles to 120 psig C₂H₄ (827 kPa) was carried out. After four hoursof reaction time, venting, quenching with 5 mL of 5% v/v HCl-acidifiedMeOH solution, and precipitation of the polymer into excess clean MeOHwere performed. The polymer products were collected by filtration,washed with additional clean MeOH, dried in a vacuum oven overnight at60° C., weighed, and analyzed. For copolymers prepared with 7-octen-1-oltrimethylsilyl ether monomer, all silyl ether units were completelyhydrolized to alcohol units during the quench procedure to give polymerscontaining 7-octen-1-ol enchainments.

[0311]¹³C and ¹H NMR spectra for polymers were obtained on a VarianINOVA 300 MHz spectrometer using a 10 mm broadband probe, a JEOL Delta400 spectrometer using a 10 mm broadband probe, or a Varian UnityPlus500 spectrometer using a 5 mm switchable probe, at 120° C. in1,1,2,2-tetrachloroethane-d₂ or 1,2-dichlorobenzene-d₄ at 120° C.Cr(acac)₃ (15 mg/mL) was used as a relaxation agent for ¹³C spectra.10,000-20,000 co-added transients were collected for ¹³C spectra and 160for ¹H NMR spectra. All alkyl branching and endgroup numbers werequantified versus the total aliphatic integral in the ¹H and ¹³C spectra(includes acetate O₂CMe but not C═O, CHOR, CHOH, or CH ₂OH peaks).Spectra were typically referenced to tetramethysilane (TMS), residualprotio solvent peaks, or major polymer resonances insensitive tocomposition (e.g. ¹³C NMR main chain unbranched methylene run CH₂, 29.98ppm). “Total alkyl branches” were quantified by ¹H NMR using the branchend CH₃ peak (1.0-0.6 ppm) and by ¹³C NMR summing all of the individualbranch types (C₁ by CH₃ at 21-18 ppm or by the two methylenes adjacentto the branch point, 39-37 ppm; C₂ by CH₃ at 13-9 ppm; C₃ by CH₃ at 14.5ppm; C₄ ⁺ by CH₃ at 14-13 ppm). In the ¹H spectra, a second set of peaksslightly downfield of 1.0 ppm, potentially corresponding to methyls nearbranch points, was not included for purposes of calculating “total alkylbranches.” These resonances were insignificant for polymers containingoctene-based monomers but more prevalent for those incorporatingnorbornene-based monomers (for the latter, inclusion of these peakswould serve to raise “total alkyl branches” to ca. 60-70/1000 carbons).For olefins and alkyl branches, “per 1000 carbons” designates olefinic,aliphatic, and acetate O₂CMe carbons only, and is equal to(1000)(14.027)/(¹H NMR M_(n)).

[0312] Olefins were quantified via the ¹H NMR resonances for vinyls(5.9-5.65 ppm and 5.3-4.85 ppm), 1,2-disubstituted olefins (5.5-5.3ppm), trisubstituted olefins (5.3-4.85 ppm, by difference from vinyls),and vinylidenes (4.85-4.55 ppm). Discrepancies between the two vinylregions (suggesting cyclic endgroups) and shifts in unassigned regionswere observed for the ethylene/norbornene copolymers; vinyl content wasdetermined from the ═CH ₂ peak (4.9 ppm) and, after correction forvinyls, the balance of the 5.9-5.65 ppm area was assigned to cyclic1,2-disubstituted structures. Non-cyclic 1,2-disubstituted olefins weredetermined from the peak at 5.5-5.3 ppm, and a peak at 5.2 ppm wasassigned as trisubstituted olefins. For ethylene/5-norbornen-2-ylacetate copolymers, the vinylidene resonance partially overlapped theexo OCH and was assumed to be zero. Vinyls, which were partiallyoverlapped in the upfield band by the endo OCH, were determined by theband at 5.9-5.65, and the appropriate area was then subtracted from theendo OCH resonance.

[0313] Number-average molecular weight (M_(n)) values calculated by ¹Hand ¹³C NMR were calculated using the olefin and aliphatic resonances(¹³C NMR: 114-140 ppm), assuming each carbon is a CH₂ (14.027 g/mol)unit and assuming one olefinic endgroup per chain. These values do notinclude contributions from groups outside of the aliphatic region (C═O,OCH, OCH₂), In most cases, signal-to-noise ratios were not sufficient toallow for a ¹³C NMR M_(n) calculation. Olefin distribution and M_(n)values for ethylene/norbornene copolymers were unavailable due todiscrepancies between the two vinyl regions (suggesting cyclicendgroups) and shifts in unassigned regions.

[0314] For purposes of copolymer compositional analysis, 1-octenecontent was determined using a ¹³C NMR by-difference method, in whichthe ratio of C₄ ⁺ branch integral to the sum of the C₁, C₂, and C₃branch integrals was calculated for the analogous homopolyethylenecontrol samples. This ratio (typically near 0.25) was multiplied by theC₁, C₂, and C₃ branch integral for the 1-octene copolymer set, and theresultant value was subtracted from the C₄ ⁺ branch integral for the1-octene copolymer set. The remainder of the C₄+branch integral was thenassigned to 1-octene. Octenyl acetate content was determined byaveraging values obtained via ¹H NMR, using the OCH ₂ resonance at 4.1ppm, and ¹³C NMR, using the OCH₂ resonance at 64.4 ppm and the C═Oresonance at 170.2 ppm. 7-Octen-1-ol (and 7-octen-1-ol trimethylsilylether) content was similarly determined, using the ¹H NMR OCH ₂resonance at 3.6 ppm, and the ¹³C NMR OCH₂ resonance at 63.4 ppm.Norbornene content was determined by averaging values obtained via ¹HNMR, using the CH resonances at 2.1-2.0 ppm, and ¹³C NMR, using thebackbone-enchained norbornene methine resonances (2 carbons at 47-48ppm) and the norbornene bridgehead methines (2 carbons at 41.5-42.0ppm). 5-Norbornen-2-yl acetate content was similarly determined, usingthe ¹H NMR OCH resonances at 4.9 (endo) and 4.65 (exo) ppm, and the ¹³CNMR OCH resonances (78.1 ppm, exo; 75.8 ppm, endo) and C═O resonances(169.8 ppm, endo; 169.4 ppm, exo). For calculated values of comonomerunits per 1000 carbons, “per 1000 carbons” designates aliphatic andacetate O₂CMe carbons only, and is equal to (1000)(mol fractioncomonomer)/[(mol fraction comonomer)(#C comonomer)+(mol fractionC₂H₄)(2)] where “#C comonomer” equals 8 for 1-octene and octenylacetate, and 7 for norbornene, 5-norbornen-2-yl acetate, 7-octen-1-ol,and 7-octen-1-ol trimethylsilyl ether.

[0315] Number-average molecular weight (M_(n)), weight-average molecularweight (M_(w)), and polydispersity index (PDI, M_(w)/M_(n)) values weremeasured using a Waters Associates 150 C high temperature gel permeationchromatograph equipped with three Polymer Laboratories mixed bed Type Bcolumns (10μ PD, 7.8 mm inner diameter, 300 mm length) in BHT(2,6-di-tert-butyl-4-methylphenol)-inhibited 1,2,4-trichlorobenzene at135° C. using an internal differential refractive index detector (1.0mL/minute flow rate; typical sample concentration 2 mg/mL; 300 μLinjection loop). Values are reported versus polyethylene standards.

[0316] In the below examples, the following abbreviations andassumptions are used in the Tables: “Total Br” is the total alkylbranches per 1000 carbons (/K) determined by summing methyls observedfor all branch types. “C₁, C₂, C₃, and C₄ ⁺” are the methyl, ethyl,propyl, and butyl and higher branches per 1000 carbons. “Vinyl,1,2-Disub., Trisub., and V-dene” are the percentages of olefin endgroupspresent as vinyl, 1,2-disubstituted olefin (vinylene), trisubstitutedolefin, and vinylidene (1,1-disubstituted) structures. “NMR M_(n)” ismolecular weight calculated assuming that all polymers have one olefinicendgroup.

Example 3

[0317] Copolymerization of ethylene and octenyl acetate using 1. Theresults in Tables 1 and 1A were obtained. TABLE 1 Activity Activity (g/M_(w)/ Ex. No. Yield (g) mmol cat) (g/mmol cat hr) M_(w) M_(n) M_(n) 3-10.65 43.33 10.83 13,590 4,170 3.26 3-2 0.65 43.33 10.83 11,940 3,8003.14 3-3 0.66 44.00 11.00 13,100 3,890 3.37 Average 0.65 43.56 10.8912,880 3,950 3.26

[0318] TABLE 1A ¹H ¹³C Avg. ¹H ¹³C Avg. mol % mol % mol % Total TotalTotal % % 1,2- % % V- C₁/ C₂/ C₃/ C₄ ⁺/ ¹H NMR Ex. No. comon. comon.comon. Br/K Br/K Br/K Vinyl Disub. Trisub. dene K K K K M_(n) 3-1 0.70.6 0.7 18.1 15.4 16.8 47.4 44.7 7.8 0 10.8 0.9 0.2 3.5 4356 3-2 0.7 0.60.7 18.7 22.4 20.6 51.0 45.5 3.5 0 12.9 3.5 0.6 5.3 4210 3-3 0.7 0.7 0.718.3 18.4 18.4 51.2 45.8 3.0 0 12.6 1.2 0.3 4.3 4319 Average 0.7 0.6 0.718.4 18.7 18.6 49.9 45.3 4.8 0 12.1 1.9 0.4 4.4 4295

Comparative Example C2

[0319] Copolymerization of ethylene and octenyl acetate using C1. Theresults in Tables 2 and 2A were obtained. TABLE 2 Activity (g/ Activity(g/ M_(w)/ Ex. No. Yield (g) mmol cat) mmol cat hr) M_(w) M_(n) M_(n)C2-1 0.509 33.93 8.48 15,840 7,390 2.14 C2-2 0.462 30.80 7.70 14,3206,150 2.33 C2-3 0.420 28.00 7.00 15,480 7,160 2.16 Average 0.464 30.917.73 15,210 6,900 2.21

[0320] TABLE 2A ¹H ¹³C Avg. ¹H ¹³C Avg. mol % mol % mol % Total TotalTotal % % 1,2- % % V- C₁/ C₂/ C₃/ C₄ ⁺/ ¹H NMR Ex. No. comon* comon.comon. Br/K Br/K Br/K Vinyl Disub. Trisub. dene K K K K M_(n) C2-1 0.91.0 1.0 21.5 24.3 22.9 29.4 70.6 0.0 0 15.2 4.8 1.0 3.3 10318 C2-2 0.91.1 1.0 22.7 25.1 23.9 29.1 70.9 0.0 0 18.5 2.5 0.6 3.4 9331 C2-3 0.90.9 0.9 22.6 21.9 22.3 25.1 66.3 8.6 0 16.1 1.9 0.8 3.2 9362 Average 0.91.0 1.0 22.3 23.8 23.0 27.9 69.3 2.9 0 16.6 3.1 0.8 3.3 9670

Example 4

[0321] Copolymerization of ethylene and 7-octen-1-ol using 1. Theresults in Tables 3 and 3A were obtained. TABLE 3 Activity (g/ ActivityM_(w)/ Ex. No. Yield (g) mmol cat) (g/mmol cat hr) M_(w) M_(n) M_(n) 4-10.05 3.33 0.83 6,610 2,650 2.49 4-2 0.05 3.33 0.83 6,870 2,680 2.56 4-30.06 4.00 1.00 6,340 2,550 2.49 Average 0.05 3.56 0.89 6,610 2,630 2.51

[0322] TABLE 3A ¹H ¹³C Avg. ¹H ¹³C Avg. mol % mol % mol % Total TotalTotal % % 1,2- % % V- C₁/ C₂/ C₃/ C₄ ⁺/ ¹H NMR Ex. No. comon. comon.comon. Br/K Br/K Br/K Vinyl Disub. Trisub. dene K K K K M_(n) 4-1 0.70.7 0.7 22.5 17.5 20.0 52.3 42.0 5.7 0 11.1 2.2 0.0 4.1 3240 4-2 0.7 NA0.7 23.0 NA 23.0 54.6 42.7 2.8 0 NA NA NA NA 3378 4-3 0.7 0.8 0.8 23.519.4 21.5 57.4 43.6 0.0 0 14.3 0.0 0.0 5.1 3381 Average 0.7 0.8 0.7 23.018.5 21.5 54.8 42.8 2.8 0 12.7 1.1 0.0 4.6 3333

Comparative Example C3

[0323] Copolymerization of ethylene and 7-octen-1-ol using C1. Theresults in Tables 4 and 4A were obtained. TABLE 4 Activity (g/ ActivityM_(w)/ Ex. No. Yield (g) mmol cat) (g/mmol cat hr) M_(w) M_(n) M_(n)C3-1 0.019 1.27 0.32 6,740 3,440 1.96 C3-2 0.006 0.40 0.10 5,500 2,7402.01 C3-3 0.014 0.93 0.23 7,510 3,720 2.02 Average 0.013 0.87 0.22 6,5833,300 2.00

[0324] TABLE 4A ¹H ¹H mol % Total % 1,2- % % V- ¹H NMR Ex. No. comon.Br/K % Vinyl Disub. Trisub. dene M_(n) C3-1 0.9 24.0 33.5 49.1 17.4 09203 C3-2 NA NA NA NA NA NA NA C3-3 0.8 24.1 39.7 60.3 0  0 10422 Average 0.9 24.1 36.6 54.7  8.7 0 9813

Example 5

[0325] Copolymerization of ethylene and 7-octen-1-ol trimethylsilylether using 1. The results in Tables 5 and 5A were obtained. TABLE 5Activity (g/ Activity (g/ M_(w)/ Ex. No. Yield (g) mmol cat) mmol cathr) M_(w) M_(n) M_(n) 5-1 0.74 49.33 12.33 12,030 3,870 3.11 5-2 0.6845.33 11.33 10,120 3,610 2.80 5-3 0.68 45.33 11.33 11,570 3,780 3.06Average 0.70 46.67 11.67 11,240 3,750 2.99

[0326] TABLE 5A Avg. ¹H mol % ¹³C mol % mol % ¹H Total ¹³C Total Avg.Total % % 1,2- % % V- C₁/ C₂/ C₃/ C₄ ⁺/ ¹H Ex. No. comon.* comon.*comon.* Br/K Br/K Br/K Vinyl Disub. Trisub. dene K K K K NMR M_(n) 5-10.7 0.6 0.7 19.5 16.7 18.1 51.9 46.4 1.7 0 11.3 0.9 0.5 4.1 4257 5-2 0.80.7 0.8 20.3 16.0 18.2 49.3 44.8 5.8 0 10.9 0.5 0.2 4.4 3880 5-3 0.7 0.60.7 19.9 17.4 18.7 49.3 44.7 6.0 0 11.1 1.0 0.5 4.7 3963 Average 0.7 0.60.7 19.9 16.7 18.3 50.2 45.3 4.5 0 11.1 0.8 0.4 4.4 4033

Comparative Example C4

[0327] Copolymerization of ethylene and 7-octen-1-ol trimethylsilylether using C1. The results in Tables 6 and 6A were obtained. TABLE 6Activity Activity (g/ M_(w)/ Ex. No. Yield (g) (g/mmol cat) mmol cat hr)M_(w) M_(n) M_(n) C4-1 0.69 46.00 11.50 17,790 8,030 2.22 C4-2 0.6744.67 11.17 18,900 8,470 2.23 C4-3 0.66 44.00 11.00 18,930 8,280 2.29Average 0.67 44.89 11.22 18,540 8,260 2.24

[0328] TABLE 6A ¹H ¹³C Avg. ¹H Avg. mol % mol % mol % Total ¹³C TotalTotal % % 1,2- % % V- C₁/ C₂/ C₃/ C₄ ⁺/ ¹H NMR Ex. No. comon* comon*comon* Br/K Br/K Br/K Vinyl Disub. Trisub. dene K K K K M_(n) C4-1 0.80.7 0.8 21.4 19.5 20.5 22.2 63.3 14.4 0 15.5 1.2 0.5 2.4 8108 C4-2 0.80.7 0.8 21.0 18.1 19.6 29.8 66.5 3.7 0 15.2 1.3 0.3 1.3 9041 C4-3 0.80.6 0.7 20.3 18.2 19.3 28.0 68.2 3.8 0 15.5 0.7 0.3 1.7 9275 Average 0.80.7 0.7 20.9 18.6 19.8 26.7 66.0 7.3 0 15.4 1.1 0.4 1.8 8808

Comparative Example C5

[0329] Copolymerization of ethylene and 1-octene using 1.Copolymerization with 1-octene was carried out to gauge the effects ofomega-polar substituents (acetate, alcohol, trimethylsilyl ether)with 1. The results in Tables 7 and 7A were obtained. TABLE 7 ActivityActivity (g/ M_(w)/ Ex. No. Yield (g) (g/mmol cat) mmol cat hr) M_(w)M_(n) M_(n) C5-1 2.05 136.67 34.17 11,390 3,610 3.16 C5-2 1.98 132.0033.00 11,720 3,790 3.09 C5-3 1.98 132.00 33.00 12,830 3,700 3.47 Average2.00 133.56 33.39 11,980 3,700 3.24

[0330] TABLE 7A ¹H ¹³C Avg. ¹H ¹³C Avg. mol % mol % mol % Total TotalTotal % % 1,2- % % V- ¹H NMR Ex. No. comon. comon. comon. Br/K Br/K Br/KVinyl Disub. Trisub. dene C₁/K C₂/K C₃/K C₄ ⁺/K M_(n) C5-1 NA 0.3 NA25.6 19.5 22.6 44.2 50.1 5.7 0 11.6 1.2 0.3 6.4 3776 C5-2 NA 0.5 NA 23.720.7 22.2 42.9 51.2 5.9 0 11.2 1.7 0.3 7.5 4304 C5-3 NA 0.6 NA 24.3 25.124.7 46.2 51.5 2.2 0 13.0 2.4 0.6 9.1 4082 Average NA 0.5 NA 24.5 21.823.2 44.4 50.9 4.6 0 11.9 1.8 0.4 7.7 4054

Comparative Example C6

[0331] Copolymerization of ethylene and 1-octene using C1.Copolymerization with 1-octene was carried out to gauge the effects ofomega-polar substituents (acetate, alcohol, trimethylsilyl ether) withC1. The results in Tables 8 and 8A were obtained. TABLE 8 Yield ActivityActivity Ex. No. (g) (g/mmol cat) (g/mmol cat hr) M_(w) M_(n)M_(w)/M_(n) Notes C6-1 2.42 161.33 40.33 9,020 2,590 3.48 sl. bimodalMWD C6-2 2.94 196.00 49.00 15,500 3,160 4.91 bimodal MWD C6-3 2.64176.00 44.00 15,280 2,880 5.31 bimodal MWD Average 2.67 177.78 44.4413,270 2,880 4.56

[0332] TABLE 8A ¹H ¹³C Avg. ¹H ¹³C Avg. mol % mol % mol % Total TotalTotal % % 1,2- % % V- ¹H NMR Ex. No. comon. comon. comon. Br/K Br/K Br/KVinyl Disub. Trisub. dene C₁/K C₂/K C₃/K C₄ ⁺/K M_(n) C6-1 NA 1.2 NA51.4 51.3 51.4 13.4 80.4 6.1 0 25.9 7.9 2.0 15.6 3122 C6-2 NA 0.8 NA44.1 45.8 45.0 13.5 80.8 5.7 0 23.5 7.3 1.9 13.1 3916 C6-3 NA 1.1 NA48.1 50.1 49.1 11.6 81.7 6.7 0 26.3 6.9 1.9 15.0 3669 Average NA 1.0 NA47.9 49.1 48.5 12.8 81.0 6.2 0 25.2 7.4 1.9 14.6 3569

Example 6

[0333] Copolymerization of ethylene and 5-norbornen-2-yl acetateusing 1. The results in Tables 9 and 9A were obtained. TABLE 9 YieldActivity Activity ¹H ¹H Ex. No. (g) (g/mmol cat) (g/mmol cat hr) M_(w)M_(n) M_(w)/M_(n) endo exo endo:exo 6-1 0.060 4.00 1.00 7,240 3,720 1.954.6 1.4 77:23 6-2 0.055 3.67 0.92 6,850 3,680 1.86 5.5 1.4 80:20 6-30.050 3.33 0.83 6,800 3,750 1.81 5.7 1.4 80:20 Average 0.055 3.67 0.926,960 3,720 1.87 5.3 1.4 79:21

[0334] TABLE 9A ¹H ¹H mol % Total % % 1,2- % % ¹H Ex. No. comon. Br/KVinyl Disub. Trisub. V-dene NMR M_(n) 6-1 5.9 14.5 58.6 41.4 0 0 44206-2 6.9 16.2 59.4 40.6 0 0 4619 6-3 7.2 14.7 59.0 41.0 0 0 4317 Average6.7 15.1 59.0 41.0 0 0 4452

Comparative Example C7

[0335] Copolymerization of ethylene and 5-norbornen-2-yl acetate usingC1. The results in Tables 10 and 10A were obtained. TABLE 10 YieldActivity (g/ Activity (g/ M_(w)/ ¹H ¹³C Avg ¹H ¹³C Avg Ex. No. (g) mmolcat) mmol cat hr) M_(w) M_(n) M_(n) endo endo endo exo exo endo endo:exoC7-1 0.110 7.33 1.83 17,500 10,520 1.66 4.8 4.5 4.7 1.4 1.4 1.4 77:23C7-2 0.087 5.80 1.45 13,530 6,920 1.96 5.3 5.8 5.6 1.6 1.7 1.7 77:23C7-3 0.104 6.93 1.73 15,130 7,800 1.94 5.5 5.4 5.5 1.7 1.7 1.7 76:24Average 0.100 6.69 1.67 15,390 8,410 1.85 5.2 5.2 5.2 1.6 1.6 1.6 77:23

[0336] TABLE 10A ¹H ¹³C Avg. ¹H ¹³C Avg. mol % mol % mol % Total TotalTotal % % 1,2- % % V- Ex. No. comon. comon. comon. Br/K Br/K Br/K VinylDisub. Trisub. dene C₁/K C₂/K C₃/K C₄ ⁺/K ¹H NMR M_(n) C7-1 6.2 5.9 6.114.5 11.3 12.9 30.3 69.7 0 0 See not not not 13126 C7-2 7.0 7.5 7.3 17.710.0 13.9 27.0 73.0 0 0 Total seen seen seen 9482 C7-3 7.2 7.1 7.2 17.19.5 13.3 29.4 70.6 0 0 Me 9629 Average 6.8 6.8 6.8 16.4 10.3 13.4 28.971.1 0 0 10746

Comparative Example C8

[0337] Copolymerization of ethylene and norbornene using 1.Copolymerization with norbornene was carried out to gauge the effects ofthe cyclic-sited acetate substituent on 1. The results in Tables 11 and11A were obtained. TABLE 11 Activity Activity M_(w)/ Ex. No. Yield (g)(g/mmol cat) (g/mmol cat hr) M_(w) M_(n) M_(n) C8-1 0.40 26.67 6.679,120 3,980 2.29 C8-2 0.35 23.33 5.83 9,400 4,450 2.11 C8-3 0.36 24.006.00 8,080 3,590 2.25 Average 0.37 24.67 6.17 8,870 4,010 2.22

[0338] TABLE 11A ¹H ¹³C Avg. mol % mol % mol % ¹H Total ¹³C Total Avg.Ex. No. comon. comon. comon. Br/K* Br/K{circumflex over ( )} Total Br/KC8-1 15.2 12.8 14.0 25.0 9.5 17.3 C8-2 14.9 13.2 14.1 26.0 9.8 17.9 C8-313.9 12.6 13.3 25.9 9.7 17.8 Average 14.7 12.9 13.8 25.6 9.7 17.7*Analysis complicated by cyclic olefinic endgroups. {circumflex over( )}¹³C by S_(αδ+) CH₂ adjacent to branch (37.1 ppm): C8-1, 12; C8-2,12; C8-3, 13. % % 1,2- % % V- ¹H NMR Ex. No. Vinyl* Disub* Trisub* dene*C₁/K C₂/K C₃/K C₄ ⁺/K M_(n)* C8-1 37.2 37.4 23.9 1.5 6.1 0.8 0.2 2.53024 C8-2 38.9 35.4 25.7 0 6.4 0.0 0.4 3.0 3408 C8-3 31.8 32.2 36.0 06.9 0.0 0.2 2.5 2781 Average 36.0 35.0 28.5 0.5 6.5 0.3 0.3 2.7 3071*Analysis complicated by cyclic olefinic endgroups. 1,2-Disub. includessome cyclics.

Comparative Example C9

[0339] Copolymerization of ethylene and norbornene using C1.Copolymerization with norbornene was carried out to gauge the effects ofthe cyclic-sited acetate substituent on C1. The results in Tables 12 and12A were obtained. TABLE 12 Yield Activity (g/ Activity M_(w)/ Ex. No.(g) mmol cat) (g/mmol cat hr) M_(w) M_(n) M_(n) C9-1 0.477 31.80 7.9525,510 13,930 1.83 C9-2 1.000 66.67 16.67 21,120 11,010 1.92 C9-3 0.61641.07 10.27 23,440 12,330 1.90 Average 0.698 46.51 11.63 23,360 12,4201.88

[0340] TABLE 12A ¹H ¹³C Avg. mol % mol % mol % ¹H Total ¹³C Total Avg.Ex. No. comon. comon. comon. Br/K* Br/K{circumflex over ( )} Total Br/KC9-1 14.9 13.0 14.0 26.3 10.9 18.6 C9-2 10.5 9.5 10.0 25.8 14.9 20.4C9-3 13.3 11.7 12.5 25.8 13.5 19.7 Average 12.9 11.4 12.2 26.0 13.119.5 * Analysis complicated by cyclic olefinic endgroups. {circumflexover ( )}¹³C by S_(αδ+) CH₂ adjacent to branch (37.1 ppm): C9-1, 14;C9-2, 21; C9-3, 16. % % 1,2- % % V- ¹H NMR Ex. No. Vinyl* Disub* Trisub*dene* C₁/K C₂/K C₃/K C₄ ⁺/K M_(n)* C9-1 23.7 54.1 19.0 3.1 8.8 1.1 0 1.010868 C9-2 28.5 57.3 12.9 1.4 9.4 2.8 0.6 2.1 10728 C9-3 22.1 50.0 27.90 9.9 1.7 0.6 1.3 8662 Average 24.8 53.8 19.9 1.5 9.4 1.9 0.4 1.5 10086*Analysis complicated by cyclic olefinic endgroups. 1,2-Disub. includessome cyclics.

Comparative Example C10

[0341] Homopolymerization of ethylene using 1. The results in Tables 13and 13A were obtained. TABLE 13 Yield Activity (g/ Activity (g/ M_(w)/Ex. No. (g) mmol cat) mmol cat hr) M_(w) M_(n) M_(n) C10-1 2.08 138.6734.67 16,990 3,690 4.60 C10-2 2.06 137.33 34.33 15,800 3,900 4.05 C10-3*1.56 104.00 26.00 14,840 3,530 4.20 Average{circumflex over ( )} 2.07138.00 34.5 16,400 3,800 4.33

[0342] TABLE 13A ¹H ¹³C Avg. Total Total Total % % 1,2- % % V- ¹H NMR¹³C Avg. Ex. No. Br/K Br/K Br/K Vinyl Disub. Trisub. dene C₁/K C₂/K C₃/KC₄ ⁺/K M_(n) NMR M_(n) NMR M_(n) C10-1 19.8 17.5 18.7 49.9 48.4 1.7 011.7 0.5 0.5 4.7 4169 3949 4059 C10-2 19.6 15.7 17.7 50.4 44.9 4.6 010.9 0.9 0.2 3.7 4216 4144 4180 C10-3* 20.9 18.7 19.8 43.3 46.6 10.2 011.5 1.6 0.5 5.2 3711 3841 3776 Average{circumflex over ( )} 19.7 16.618.2 50.2 46.7 3.2 0 11.3 0.7 0.4 4.2 4193 4047 4120

Comparative Example C11

[0343] Homopolymerization of ethylene using C1. The results in Tables 14and 14A were obtained. TABLE 14 Activity (g/ Activity (g/ M_(w)/ Ex. No.Yield (g) mmol cat) mmol cat hr) M_(w) M_(n) M_(n) C11-1 2.404 160.2740.07 12,760 2,780 4.59 C11-2 2.446 163.07 40.77 16,580 2,870 5.78 C11-32.708 180.53 45.13 16,970 3,280 5.17 Average 2.519 167.96 41.99 15,4402,980 5.18

[0344] TABLE 14A ¹H ¹³C Avg. Total Total Total % % 1,2- % % V- ¹H NMREx. No. Br/K Br/K Br/K Vinyl Disub. Trisub. dene C₁/K C₂/K C₃/K C₄ ⁺/KM_(n) C11-1 48.7 50.3 49.5 14.7 80.2 5.2 0 29.5 8.2 1.8 10.8 3287 C11-244.6 46.7 45.7 14.5 85.5 NA* 0 27.7 7.5 1.6 9.9 4026 C11-367.4{circumflex over ( )} 41.4{circumflex over ( )} 54.4 12.1 81.1 6.8 025.0 6.6 1.3 8.5 2042 Average 53.6 46.1 49.9 13.8 82.3 6.0 0 27.4 7.41.6 9.7 3118

[0345] Table 15 summarizes all ethylene/polar monomer copolymizerationresults for azo-phenoxide catalyst 1 (1.0 mM 1, 0.4 M comonomer, toluenesolvent, 4 h, 50° C., 120 psig C₂H₄ (827 kPa)). C2/ C2/C8— C2/ C2/Comonomer C2 only C2/C8 C2/NB C8—Ac OSiMe₃{circumflex over ( )} C8—OHNB—Ac Activity, 138.00 133.56 24.67 43.56 46.67 3.56 3.67 g/mmol 1 M_(w)16,400 11,980 8,870 12,880 11,240 6,610 6,960 M_(n) 3,800 3,700 4,0103,950 3,750 2,630 3,720 M_(w)/M_(n) 4.33 3.24 2.22 3.26 2.99 2.51 1.87¹H NMR 4,120 4,050 3,070 4,300 4,030 3,330 4,450 M_(n) Comon — 0.5 13.80.7 0.7 0.7 6.7 mol % Olefins* 3.3 3.5 4.6 3.3 3.5 4.2 3.2 Comon. — 2.551.3 3.4 3.4 3.4 28.7 units* % V:1,2:Tri:VD 50:47:3:0 44:51:5:036:35:29:1 50:45:5:0 50:45:5:0 55:43:3:0 59:41:0:0 C₁:C₂:C₃:C₄ ⁺*11:1:0:4 12:2:0:8 7:0:0:3 12:2:0:4 11:1:0:4 13:1:0:5 — Total ¹H 19.724.5 25.6 18.4 19.9 23.0 15.1 Br* Total ¹³C 16.6 21.8 9.7 18.7 16.7 18.5— Br*

[0346] Table 16 summarizes all ethylene/polar monomer copolymerizationresults for comparative imine-phenoxide catalyst C1 (1.0 mM C1, 0.4 Mcomonomer, toluene solvent, 4 h, 50° C., 120 psig C₂H₄ (827 kPa)). C2/C2/C8— C2/ C2/ Comonomer C2 only C2/C8 C2/NB C8—Ac OSiMe₃{circumflexover ( )} C8—OH NB—Ac Activity, 167.96 177.78 46.51 30.91 44.89 0.876.69 g/mmol C1 M_(w) 15,440 13,270 23,360 15,210 18,540 6,580 15,390M_(n) 2,980 2,880 12,420 6,900 8,260 3,300 8,410 M_(w)/M_(n) 5.18 4.561.88 2.21 2.24 2.00 1.85 ¹H NMR 3,120 3,570 10,090 9,670 8,810 9,81010,750 M_(n) Comon — 1.0 12.2 1.0 0.7 0.9 6.8 mol % Olefins* 4.5 3.9 1.41.5 1.6 1.4 1.3 Comon. — 4.9 46.7 4.7 3.7 4.2 29.3 units* % V:1,2:Tri:VD14:82:6:0 12:81:6:0 25:54:20:2 28:69:3:0 27:66:7:0 37:55:9:0 29:71:0:0C₁:C₂:C₃:C₄ ⁺* 27:7:2:10 25:7:2:15 9:2:0:2 17:3:1:3 15:1:0:2 — 10:0:0:0Total ¹H 53.6 47.9 26.0 22.3 20.9 24.1 16.4 Br* Total ¹³C 46.1 49.1 13.123.8 18.6 — 10.3 Br*

Example 7

[0347] Comparison of retention of activity and comonomer incorporationupon introduction of functional groups for 1 and C1. Table 17 showsaverage catalyst activity for 1 and C1 in the presence of polarcomonomers, as a percentage of the base activity seen with theunfunctionalized monomer of similar structure (e.g., octenyl acetate to1-octene). Table 17 also shows comonomer incorporation for 1 and C1, asa percentage of the base incorporation seen with the unfunctionalizedmonomer. Azo-phenoxide 1 gives less severe activity drops uponfunctionalization of an octene or norbornene comonomer framework thanimine-phenoxide C1. For the case of octene-based functional comonomers,an increase in comonomer incorporation in seen with 1, rather than adecrease as is seen for C1.

[0348] Table 17. Activity/activity retention (in %) and comonomerincorporation/incorporation retention (%) for polar monomers vs.analogous unfunctionalized monomers for 1 and C1 (toluene solvent, 4 h,50° C., 120 psig C₂H₄ (827 kPa)). Average Activity, Average Comonomer gPE/mmol Incorporation, mol % Copoly- cat (% of base) (% of base)merization 1 C1 1 C1 C2/C8 133.56 177.78  0.5  1.0 (base case) C2/C8— 43.56 (33%)  30.91 (17%)  0.7 (140%)  1.0 (100%) Ac C2/C8—  3.56 (3%) 0.87 (0.5%)  0.7 (140%)  0.9 (90%) OH C2/C8-  46.67 (35%)  44.89 (25%) 0.7 (140%)  0.7 (70%) OSiMe₃{circumflex over ( )} C2/NB  24.67  46.5113.8 12.2 (base case) C2/NB—  3.67 (15%)  6.69 (14%)  6.7 (49%)  6.8(55%) Ac

Example 8

[0349] Comparison of retention of copolymer molecular weight uponintroduction of functional groups for 1 and C1. Table 18 shows averagecopolymer weight-average molecular weight (Mw) for 1 and C1 in thepresence of polar comonomers, as a percentage of the base Mw seen withthe unfunctionalized monomer of similar structure. Mw values forfunctional copolymers are not directly comparable to those for baseunfunctionalized (C2/C8 or C2/NB) copolymers due to changes inrefractive index. However, as copolymer compositions are roughly similarbetween 1 and C1 for each particular comonomer, Mw values/percentagesfor each can be compared between the two catalysts. The reduction incopolymer Mw upon adding an acetate functionality to a norbornenemonomer is less severe for 1 than for C1. A similar (but smaller)advantage for 1 exists upon addition of an alcohol group to an octenecomonomer. TABLE 18 Mw and Mw retention (in %) for polar monomers vs.analogous unfunctionalized monomers for 1 and C1 (toluene solvent, 4 h,50° C., 120 psig C₂H₄ (827 kPa)). Average Mw^(a) (% of base)Copolymerization 1 C1 C2/C8 (base case) 11,980 13,270 C2/C8—Ac 12,880(108%) 15,210 (115%) C2/C8—OH  6,610 (55%)  6,580 (50%)C2/C8—OSiMe₃{circumflex over ( )} 11,240 (94%) 18,540 (140%) C2/NB (basecase)  8,870 23,360 C2/Nb—Ac  6,960 (87%) 15,390 (66%)

Example 9

[0350] Comparison of alkyl branches per 1000 carbons and vinyl endgroupcontent for ethylene/polar monomer copolymers made with 1 and C1. Table19 shows the average total alkyl branch content, and percent ofendgroups that are vinyl structures, for ethylene/polar monomercopolymers made with 1 and C1. The functional copolymers prepared with 1have fewer alkyl branches than those prepared with C1, and also have agreater percentage of their olefin endgroups as vinyls. TABLE 19 Totalalkyl branches (per 1000 carbons) and vinyl endgroup content (as %) forethylene/polar monomer copolymers made with 1 and C1 (toluene solvent, 4h, 50° C., 120 psig C₂H₄ (827 kPa)). Average Br/ Average % 1000 C^(a)Vinyls^(b) Copolymerization 1 C1 1 C1 C2/C8—Ac 18.4 22.3 49.9 27.9C2/C8—OH 23.0 24.1 54.8 36.6 C2/C8—OSiMe₃{circumflex over ( )} 19.9 20.950.2 26.7 C2/Nb—Ac 15.1 16.4 59.0 28.9

Example 10

[0351] Synthesis of ethylene/5-norbornen-2-ol copolymer viacopolymerization of ethylene/5-norbornen-2-yl acetate using 1. A set ofthree triplicate copolymerizations similar to Example 6 were carriedout, using a polar monomer feed of 2 mmol (0.13 M) 5-norbornen-2-ylacetate per cell instead of 6 mmol. After isolation and weighing, thethree separate batches of copolymer were combined for compositionalanalysis. In a 250 mL 3-necked 24/40 round bottom flask equipped with amechanical stirrer and a reflux condenser, 1.7 g of the copolymer wasdissolved in 50 mL toluene. Using an addition funnel, a solution of 150mg KOH dissolved in 20 mL methanol/1 mL H₂O was added dropwise to thestirred solution over a 30 minute period under N₂. The mixture wasstirred overnight at 118° C. and the product polymer(polyethylene-co-5-norbornen-2-ol) was subsequently precipitated intomethanol, washed, filtered, dried, and characterized similarly toprevious examples (1.6 g). IR (KBr pellet): 3332 cm⁻¹ (w, O—H); no C═Ostretch at 1700-1600 cm⁻¹. The results in Tables 20 and 20A wereobtained.

[0352] Tables 20 and 20A (Example 10)—Ethylene/5-norbornen-2-yl acetatecopolymerization with 1 and hydrolysis of product toethylene/5-norbornen-2-ol copolymer. TABLE 20 Yield Activity Activity ¹Hmol % Ex. No. (g) (g/mmol cat) (g/mmol cat hr) M_(w) M_(n) M_(w)/M_(n)comon. 10-1 0.65 43.33 10.83 10-2 0.582 38.80 9.70 10-3 0.542 36.13 9.03Average 0.591 39.42 9.86 9,800* 4,430* 2.22* 1.9*

[0353] TABLE 20A ¹H Ex. Total % % 1,2- % % V- ¹H ¹H No. Br/K VinylDisub. Trisub. dene endo exo endo:exo Avg* 13.1 56.0 44.0 0 0 1.3 0.669:31

[0354] For the examples below, NMR characterization ofethylene/5-norbornen-2-ol copolymers was carried out similarly to theanalyses previously described for other copolymers. ¹H NMR copolymercomposition was determined using the CHOH resonances at 4.4 (endo) and3.9 (exo) ppm. ¹³C NMR copolymer composition was determined using theCHOH resonances at 75.4 ppm (exo) and 73 ppm (endo). ¹³C NMR alkylbranching per 1000 carbons does not include chain ends and wasdetermined by summing contributions from 1B₁ methyls (20 ppm) and 1B₃₊branch methyls (14.1 ppm, after subtracting contributions from linearmethyl chain ends as measured by the 2 s methylene peak at 22.9 ppm; no1B₂ methyls were detected). Differential scanning calorimetry (DSC) wascarried out on a TA Instruments 2920 calorimeter using a scan rate of 10degrees per minute. Melting point (T_(m)) values are maxima derived fromsecond heats. Molecular weights (Mw, Mn, Mw/Mn) were measured aspreviously described for other copolymers. 5-Norbornen-2-ol (AldrichChemical Co.) was purified prior to use by dissolution in hot, dryhexanes, followed by filtration and recrystallization at −40° C.

Example 11 Ethylene/5-norbornen-2-yl acetate copolymerization withazo-phenoxide catalyst 1 at lower ethylene pressure.

[0355] In a drybox, a 300 cc Hasteloy C Parr reactor bottom was chargedwith 2.23 g (14.6 mmol) of 5-norbornen-2-yl acetate, 70 mL dry toluene,and 20 mL dry diethyl ether. Separately, 56.5 mg (0.065 mmol) of 1 wasdissolved in 10 mL dry toluene in a scintillation vial. This solutionwas loaded into an airtight 10 mL syringe and kept in the drybox untilimmediately before use. The reactor was sealed with a head apparatusfeaturing a mechanical stirring paddle and a catalyst injection valveand removed from the drybox. The contents of the reactor werepressurized with 100 psig ethylene (690 kPa), stirred for 3 minutes, andthe reactor was vented and heated to 40° C. The catalyst solution wasthen injected into the reactor, which was pressurized to a constant 50psig (348 kPa) using a pressure vessel tank (PVT) and stirred for 2hours. Subsequently, the reactor was vented and cooled, and 5 mLmethanol was added via syringe to terminate polymerization. The contentsof the reactor were added to an excess of methanol, and the solidpolymer was collected by filtration, washed with additional cleanmethanol, and dried in a vacuum oven overnight at 60 C. Results aregiven in Tables 21 and 21A.

Comparative Example C12

[0356] Ethylene/5-norbornen-2-yl acetate copolymerization withimine-phenoxide catalyst C1 at lower ethylene pressure. This procedurewas carried out in a similar manner to Example 11 except that theinitial charge of ethylene was held for 5 minutes prior to venting. Theamounts of reagents used were: 53 mg (0.062 mmol) C1 in 5 mL toluene(catalyst solution); 2.23 g (14.6 mmol) 5-norbornen-2-yl acetate, 75 mLtoluene, and 20 mL diethyl ether (in Parr). Results are given in Tables21 and 21A.

Example 12

[0357] Ethylene/5-norbornen-2-ol copolymerization with azo-phenoxidecatalyst 1 at lower ethylene pressure. This procedure was carried out ina similar manner to Example 11 except that the initial charge ofethylene (prior to venting) was 50 psig. The amounts of reagents usedwere 43.5 mg (0.05 mmol) azo-phenoxide 1 in 10 mL toluene (catalystsolution); 1.58 g (14.4 mmol) 5-norbornen-5-ol, 54 mL toluene, and 16 mLdiethyl ether (in Parr). Results are given in Tables 21 and 21A.

Comparative Example C13

[0358] Ethylene/5-norbornen-2-ol copolymerization with imine-phenoxidecatalyst C1 at lower ethylene pressure. This procedure was carried outin a similar manner to Example 11 except that the initial charge ofethylene was held for 5 minutes prior to venting. The amounts ofreagents used were: 55 mg (0.065 mmol) C1 in 5 mL toluene (catalystsolution); 2.0 g (18.2 mmol) 5-norbornen-2-ol, 75 mL toluene, and 20 mLdiethyl ether (in Parr). Results are given in Tables 21 and 21A. Tables21 and 21A Ethylene copolymerization with 5-norbornen-2-yl acetate(NB—Ac) or 5-norbornen-2-ol (NB—OH) using 1 and C1 (40° C., 50 psig C₂H₄(348 kPa), 2 h). Catalyst Comonomer Yield Activity (g PE/ Mol % Ex. No.(mmol) (mmol) Solvent (g) mmol cat) comon. 11 1 (0.065) NB—Ac (14.6) 80mL toluene 0.9 13.8 5.9^(a) 20 mL Et₂O C12 C1 (0.062) NB—Ac (14.6) 80 mLtoluene 1.61 26.0 3.7^(a) 20 mL Et₂O 12 1 (0.050) NB—OH (14.4) 64 mLtoluene 0.26 5.2 7.0^(b) 16 mL Et₂O C13 C1 (0.065) NB—OH (18.2) 80 mLtoluene 0.63 97 6.3^(b) 20 mL Et₂O ^(a)By ¹³C NMR. ^(b)By average of ¹Hand ¹³C NMR. Table 21A Alkyl Br/ Ex. No. endo:exo 1000 C^(c) Mw/Mn(PDI)^(d) T_(m) ^(e) (° C.) 11 76:24^(c) 13.6  4,560/2,420 (1.9) 72.1 v.broad C12 NA 11.6^(f) 19,780/7,580 (2.6) 90.3 broad, lo-temp shoulder 1274:26^(b) 14.5  3,290/1,600 (2.1) 77.6 broad, lo-temp shoulder C1372:28^(a) 13.7^(f)  9,980/5,640 (1.8) 83.6 v. broad ^(a)By ¹H NMR.^(b)By average of ¹H and ¹³C NMR. ^(c)By ¹³C NMR; linear chain ends notincluded. ^(d)DRI, vs. polyethylene standards, in 1,2,4-trichlorobenzeneat 135° C. ^(e)2^(nd) Heat maxima. ^(f)Only C₁ branches detected.

[0359] Tables 17-19 (Examples 7-9) and 21 (Examples 11-12) serve toillustrate some of advantages of E-phenoxide catalysts for thecopolymerization of olefins with polar monomers. Many known olefinpolymerization catalysts show large and undesirable decreases inefficiency, as measured by reduced activity and polymer molecularweight, upon the introduction of polar monomers to the feed.Azo-phenoxide 1 gives less severe activity drops upon the addition offunctionality to an octene or norbornene comonomer framework thanimine-phenoxide C1 at 50° C. and 120 psig C₂H₄ (827 kPa). At theseconditions, azo-phenoxide 1 also shows smaller decreases in polymer Mwupon the addition of some functionalities to an octene or norbornenecomonomer framework as compared to C1. Additionally, at 40° C. and 50psig ethylene (348 kPa), 1 gives greater incorporation of5-norbornen-2-yl acetate and 5-norbornen-2-ol than C1. Thus, on arelative basis, azo-phenoxide catalyst 1 can exhibit greater activity topolar monomers, or retain more of its desirable properties for thepreparation of olefin polymers, than a similar imine-phenoxide catalyst(C1).

[0360] Additionally, at 50° C. and 120 psig C₂H₄ (827 kPa), thefunctional copolymers prepared with 1 have slightly fewer alkyl branchesthan those prepared with C1 and also have a greater percentage of theirolefin endgroups as vinyls. Reduced alkyl branching is desirable becausemany polymer properties (including melting point and crystallinity) aredegraded by the presence of branches, whereas greater vinyl endgroupcontent presents an advantage for the potential use of the functionalcopolymers prepared with 1 as macromonomers.

[0361] All documents described herein are incorporated by referenceherein, including any priority documents and/or testing procedures. Asis apparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby.

1. A polymerization method comprising contacting one or more polar monomers and one or more olefin monomers with a catalyst system comprising: 1) optionally, an activator, and 2) a catalyst composition represented by the formula:

M is selected from groups 3-11 of the periodic table; E is nitrogen or phosphorus; Ar⁰ is arene; R¹-R⁴ are, each independently, selected from hydrogen, hydrocarbyl, substituted hydrocarbyl or functional group, provided however that R³ and R⁴ do not form a naphthyl ring; L¹ represents a formal anionic ligand, L² represents a formal neutral ligand, a is an integer greater than or equal to 1; b is an integer greater than or equal to 0; and c is an integer greater than or equal to
 1. 2. The method of claim 1 wherein M is a group 4 or 10 metal.
 3. The method of claim 1 wherein M is titanium or nickel.
 4. The method of claim 1 wherein E is nitrogen.
 5. The method of claim 1 wherein a is 1, 2, 3, or
 4. 6. The method of claim 1 wherein a is 1 or
 2. 7. The method of claim 1 wherein b is 0, 1 or 2 and c is 1 or
 2. 8. The method of claim 1 wherein Ar⁰ is selected from the group consisting of ZETA-ARENES.
 9. The method of claim 1 further comprising an activator.
 10. The method of claim 1 wherein each L² is, independently, selected from the group consisting of ethers, ketones, esters, alcohols, carboxylic acids, amines, imines, azo, nitriles, heterocycles, phosphines, thioethers, alkyls, alkenes, alkynes, arenes and combinations thereof; and each L¹ is, independently, selected from the group consisting of hydrides, fluorides, chlorides, bromides, iodides, alkyls, aryls, alkenyls, alkynyls, allyls, benzyls, acyls, trimethylsilyls and combinations thereof; Ar⁰ is selected from the group consisting of substituted or unsubstituted heterocyclics, polyheterocyclics, heterocyclic ring assemblies, fused heterocyclic ring systems or combinations thereof.
 11. The method of claim 10 wherein M is nickel or titanium.
 12. The method of claim 11 wherein a=1 or 2, b=0, 1 or 2, and c=1 or
 2. 13. The method of claim 10 further comprising an activator.
 14. The method of claim 1 wherein L¹ is selected from the group consisting of ZETA-FORMAL ANIONIC LIGANDS, and L² is selected from the group consisting of ZETA-FORMAL NEUTRAL LIGANDS.
 15. The method of claim 1 wherein L¹ is selected from the group consisting of —F, —Cl, —Br, —I, —N(CH₃)₂, —OCH₃, —H, —CH₃, —C₆H₅, -allyl, -benzyl, —CH₂Si(CH₃)₃.
 16. The method of claim 1 wherein the catalyst composition is represented by one of the following formulae: (L⁰)_(a)(L¹)_(b-2)(L²)_(c)M(R⁵)₂ (L⁰)_(a)(L¹)_(b-2)(L²)_(c)M(R⁵)₁(L³)₁ (L⁰)_(a)(L¹)_(b-2)(L²)_(c)M(L³)₂ 2 3 4 (L⁰)_(a)(L²)_(c)M (L⁰)_(a)(L¹)_(b-1)(L²)_(c)M(R⁵)₁ (L⁰)_(a)(L¹)_(b-1)(L²)_(c)M(L³)₁ 5 6 7

wherein: M is selected from groups 3-11 of the periodic table, L⁰ represents an E-phenoxide ligand represented by the formula:

L¹ represents a formal anionic ligand; L² represents a formal neutral ligand; L³ represents a formal anionic ligand that comprises a functional group; a is 1, 2, 3 or 4; b is 0, 1, 2, 3, 4, 5 or 6, provided that b is not 0 or 1 in formula 2, 3 or 4 and b is not 0 in formula 6 or 7; c is 1, 2, 3 or 4; E is nitrogen or phosphorus; Ar⁰ is an arene selected from the group consisting of ZETA-ARENES; R¹-R⁴ are each independently hydrogen, a hydrocarbyl, a substituted hydrocarbyl or a functional group, provided that R³ and R⁴ do not form a naphthyl ring; and R⁵ is a hydride, a hydrocarbyl or a substituted hydrocarbyl.
 17. The method of claim 16 wherein E is nitrogen and M is titanium or nickel.
 18. The method of claim 1 wherein the catalyst composition is represented by one of the following formulae:

E is nitrogen or phosphorus; Ar¹ is selected from the group consisting of:

R¹-R⁴ are each independently hydrogen, a hydrocarbyl, a substituted hydrocarbyl or a functional group, provided that R³ and R⁴ do not form a naphthyl ring; L¹ represents a formal anionic ligand selected from the group consisting of ZETA-FORMAL ANIONIC LIGANDS; L² represents a formal neutral ligand selected from the group consisting of ZETA-FORMAL NEUTRAL LIGANDS; “d” is 1, 2 or 3; A⁻ is an anion that may or may not coordinate to Ni; and Z⁺ is a cation selected from the group consisting of metals or metal complexes of groups 1, 2, 11, and 12, Where Me is methyl, Et is ethyl, iPr is isopropyl, tBu is tertiary butyl, Ph is phenyl, p-t-BuPh is para-tertiary-butylphenyl.
 19. The method of claim 18 wherein A⁻ is a non-coordinating anion.
 20. The method of claim 18 wherein A⁻ is selected from the group consisting of halides, carboxylates, phosphates, sulfates, sulfonates, borates, aluminates, alkoxides, thioalkoxides, anonic substituted hydrocarbons, and anionic metal complexes.
 21. The method of claim 1 wherein the catalyst composition is represented by formula:

wherein L¹ represents a formal anionic ligand; R³ is hydrogen, a hydrocarbyl, a substituted hydrocarbyl or a functional group; R⁶ is C(R⁷)_(e), e is 2 or 3, R⁷ is a hydrocarbon, a substituted hydrocarbon, or a functional group, two R⁷ groups may be part of a common arene ring when e is 2; Ar¹ is an arene; and L⁴ is a formal neutral ligand, coordinated to the nickel in addition to the nitrogen of the azo-phenoxide ligand.
 22. The method of claim 21 wherein L⁴ selected from the group consisting of: P(C₆H₅)₃ P(C₁₀H₇)₃ NC—CH₃ NC—C₆H₃(CF₃)₂ CH₂═CH₂

where Me is methyl.
 23. The method of claim 22 wherein R⁶ is selected from the group consisting of t-butyl, adamantyl, phenyl, naphthyl, and anthracenyl.
 24. The method of claim 1 wherein the catalyst composition is represented by the formula:

wherein: L⁴ represents a formal neutral ligand based on carbon, nitrogen or phosphorus; R⁸ represents a formal anionic ligand which may be hydrogen or a hydrocarbyl; Ar² is a phenyl group independently substituted in the 2 and 6 positions by secondary hydrocarbons, secondary substituted hydrocarbons, tertiary hydrocarbons, tertiary substituted hydrocarbons, or arenes Ar² is an arene; Ar³ is an arene; and Me is methyl.
 25. The method of claim 24 wherein Ar² is selected from the group consisting of:

where iPr is isopropyl, tBu is tertiary butyl and Ph is phenyl.
 26. The method of claim 24 wherein Ar³ is selected from the group consisting of:


27. The method of claim 24 wherein R⁸ is selected from the group consisting of hydrogen, a hydride, methyl, ethyl, trimethylsilylmethyl, trimethylsilyl, phenyl, naphthyl, allyl and benzyl.
 28. The method of claim 1 wherein the catalyst composition is represented by the formula:

where R is anthracene and R′ is methyl or tertiary butyl, iPr is isopropyl and Ph is phenyl.
 29. The method of claim 1 wherein the olefin monomer comprises a C2 to C40 olefin monomer and the polar monomer is selected from the group consisting of carbon monoxide, 3-buten-1-ol, 2-methyl-3-buten-1-ol, 3-butene-1,2-diol, 4-penten-1-ol, 4-pentene-1,2-diol, 5-hexen-1-ol, 5-hexene-1,2-diol, 6-hepten-1-ol, 6-heptene-1,2-diol, 7-octen-1-ol, 7-octene-1,2-diol, 8-nonen-1-ol, 8-nonene-1,2-diol, 9-decen-1-ol, 9-decene-1,2-diol, 10-undecen-1-ol, 10-undecene-1,2-diol, 11-dodecen-1-ol, 11-dodecene-1,2-diol, 12-tridecen-1-ol, 12-tridecene-1,2-diol, 4-(3-butenyl)-2,2-dimethyldioxolane, 1,2-epoxy-3-butene (butadiene monoxide), 2-methyl-2-vinyloxirane, 1,2-epoxy-4-pentene, 1,2-epoxy-5-hexene, 1,2-epoxy-6-heptene, 1,2-epoxy-7-octene, 1,2-epoxy-8-nonene, 1,2-epoxy-9-decene, 1,2-epoxy-10-undecene, 1,2-epoxy-11-dodecene, 1,2-epoxy-12-tridecene, 3-buten-1-ol methyl ether, 4-penten-1-ol methyl ether, 5-hexen-1-ol methyl ether, 6-hepten-1-ol methyl ether, 7-octen-1-ol methyl ether, 8-nonen-1-ol methyl ether, 9-decen-1-ol methyl ether, 10-undecen-1-ol methyl ether, 11-dodecen-1-ol methyl ether, 12-tridecen-1-ol methyl ether, 4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, trans-2,4-pentadienoic acid, 2,6-heptadienoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, methyl 4-pentenoate, methyl 5-hexenoate, methyl 6-heptenoate, methyl 7-octenoate, methyl 8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate, ethyl 10-undecenoate, methyl 11-dodecenoate, methyl 12-tridecenoate, 3-butenyl acetate, pentenyl acetate, hexenyl acetate, heptenyl acetate, octenyl acetate, nonenyl acetate, decenyl acetate, undecenyl acetate, dodecenyl acetate, tridecenyl acetate, 4-pentene-1-nitrile, 5-hexene-1-nitrile, 6-heptene-1-nitrile, 7-octene-1-nitrile, 8-nonene-1-nitrile, 9-decene-1-nitrile, 10-undecene-1-nitrile, 11-dodecene-1-nitrile, 12-tridecene-1-nitrile, 3-buten-1-ol trimethylsilyl ether, 4-penten-1-ol trimethylsilyl ether, 5-hexen-1-ol trimethylsilyl ether, 6-hepten-1-ol trimethylsilyl ether, 7-octen-1-ol trimethylsilyl ether, 8-nonen-1-ol trimethylsilyl ether, 9-decen-1-ol trimethylsilyl ether, 10-undecen-1-ol trimethylsilyl ether, 11-dodecen-1-ol trimethylsilyl ether, 12-tridecen-1-ol trimethylsilyl ether, 2,2-dimethyl-4-pentenal, undecylenic aldehyde, 2,4-dimethyl-2,6-heptadienal, 5-hexen-2-one, nonafluoro-1-hexene, 5-norbornene-2-carbonitrile, 5-norbornene-2-carboxaldehyde, 5-norbornene-2-carboxylic acid, cis-5-norbornene-endo-2,3-dicarboxylic acid, cis-5-norbornene-2-endo-3-exo-dicarboxylic acid, 5-norbornene-2-carboxylic acid methyl ester, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, cis-5-norbornene-exo-2,3-dicarboxylic anhydride, 5-norbornene-2-endo-3-endo-dimethanol, 5-norbornene-2-endo-3-exo-dimethanol, 5-norbornene-2-exo-3-exo-dimethanol, 5-norbornene-2,2,-dimethanol, 5-norbornene-2-methanol, 5-norbornen-2-ol, 5-norbornen-2-ol trimethylsilyl ether, 5-norbornen-2-ol methyl ether, 5-norbornen-2-yl acetate, 1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ^(3,9).1^(5,15).1^(7,13)]octasiloxane, 2-benzoyl-5-norbornene, tricyclo[4.2.1.0^(0,0),]non-7-ene-3-carboxylic acid tert-butyl ester, tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxylic acid tert-butyl ester, tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxylic acid anhydride, N-butyl-tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxyimide, 2-cyclopenten-1-one ethylene ketal, and vinylene carbonate.
 30. The method of claim 1 in which the olefin monomer is ethylene and the polar monomer is 7-octen-1-ol.
 31. The method of claim 1 in which the olefin monomer is ethylene and the polar monomer is 7-octen-1-ol trimethylsilyl ether.
 32. The method of claim 1 in which the olefin monomer is ethylene and the polar monomer is octenyl acetate.
 33. The method of claim 1 in which the olefin monomer is ethylene and the polar monomer is 5-norbornen-2-yl acetate.
 34. The method of claim 1 in which the olefin monomer is ethylene and the polar monomer is 5-norbornen-2-ol and or norbornen-2-ol trimethylsilyl ether.
 35. The method of claim 1 in which the catalyst composition comprises [2-(2′,6′-Diisopropylphenylazo)-4-methyl-6-(9-anthracenyl)phenoxide]-Nickel(phenyl)(triphenylphosphine).
 36. The method of claim 29 in which the catalyst composition comprises [2-(2′,6′-Diisopropylphenylazo)-4-methyl-6-(9-anthracenyl)phenoxide]-Nickel(phenyl)(triphenylphosphine).
 37. The method of claim 1 wherein the polar monomer is present in the polymer at 0.2 to 30 mole %.
 38. The method of claim 1 wherein the polar monomer is present in the polymer at 0.2 to 15 mole %.
 39. The method of claim 1 wherein the polar monomer is present in the polymer at 5 to 15 mole %.
 40. The method of claim 1 wherein the polymerization is conducted at a temperature of 40° C. or more.
 41. The method of claim 1 wherein the polymerization is conducted at a temperature of 50° C. or more.
 42. The method of claim 1 wherein the polymerization is conducted at a pressure of 0.1 MPa or more.
 43. The method of claim 1 wherein the polymerization is conducted at a pressure of 0.25 MPa or more.
 44. The method of claim 1 wherein the polymerization is conducted in the presence of a solvent or diluent.
 45. The method of claim 1 wherein the polymerization is conducted in the presence of a solvent or diluent where the solvent or diluent comprises a mixture of a polar solvent or diluent and a non-polar solvent or diluent.
 46. The method of claim 1 wherein the polymerization is conducted at a temperature above 70° C. and a pressure above 5 MPa.
 47. The method of claim 1 wherein the polymerization is conducted in the gas phase.
 48. The method of claim 1 wherein the polymerization is conducted in the slurry phase.
 49. The method of claim 1 wherein the polymerization is conducted in the solution phase.
 50. The method of claim 1 wherein the polymerization is conducted in the presence of a mixture of toluene and diethyl ether.
 51. A copolymer comprising olefin monomer and from 0.2 to 30 mole % of a polar monomer where the copolymer has less than 25 total alkyl branches per 1000 carbons and 45% or more of its olefinic end groups as vinyls.
 52. The copolymer of claim 51 wherein the polar monomer is present in the polymer at 0.2 to 15 mole %.
 53. The copolymer of claim 51 wherein the copolymer has 50% or more of its olefinic end groups as vinyls.
 54. The copolymer of claim 51 wherein the copolymer has 55% or more of its olefinic end groups as vinyls.
 55. The copolymer of claim 51 wherein the olefin monomer comprises ethylene.
 56. The copolymer of claim 51 wherein the olefin monomer comprises propylene.
 57. The copolymer of claim 51 wherein the olefin monomer comprises ethylene and propylene.
 58. The copolymer of clam 51 wherein the olefin monomer comprises a C2 to C40 olefin monomer and the polar monomer is selected from the group consisting of carbon monoxide, 3-buten-1-ol, 2-methyl-3-buten-1-ol, 3-butene-1,2-diol, 4-penten-1-ol, 4-pentene-1,2-diol, 5-hexen-1-ol, 5-hexene-1,2-diol, 6-hepten-1-ol, 6-heptene-1,2-diol, 7-octen-1-ol, 7-octene-1,2-diol, 8-nonen-1-ol, 8-nonene-1,2-diol, 9-decen-1-ol, 9-decene-1,2-diol, 10-undecen-1-ol, 10-undecene-1,2-diol, 11-dodecen-1-ol, 11-dodecene-1,2-diol, 12-tridecen-1-ol, 12-tridecene-1,2-diol, 4-(3-butenyl)-2,2-dimethyldioxolane, 1,2-epoxy-3-butene (butadiene monoxide), 2-methyl-2-vinyloxirane, 1,2-epoxy-4-pentene, 1,2-epoxy-5-hexene, 1,2-epoxy-6-heptene, 1,2-epoxy-7-octene, 1,2-epoxy-8-nonene, 1,2-epoxy-9-decene, 1,2-epoxy-10-undecene, 1,2-epoxy-11-dodecene, 1,2-epoxy-i 2-tridecene, 3-buten-1-ol methyl ether, 4-penten-1-ol methyl ether, 5-hexen-1-ol methyl ether, 6-hepten-1-ol methyl ether, 7-octen-1-ol methyl ether, 8-nonen-1-ol methyl ether, 9-decen-1-ol methyl ether, 10-undecen-1-ol methyl ether, 11-dodecen-1-ol methyl ether, 12-tridecen-1-ol methyl ether, 4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, trans-2,4-pentadienoic acid, 2,6-heptadienoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, methyl 4-pentenoate, methyl 5-hexenoate, methyl 6-heptenoate, methyl 7-octenoate, methyl 8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate, ethyl 10-undecenoate, methyl 11-dodecenoate, methyl 12-tridecenoate, 3-butenyl acetate, pentenyl acetate, hexenyl acetate, heptenyl acetate, octenyl acetate, nonenyl acetate, decenyl acetate, undecenyl acetate, dodecenyl acetate, tridecenyl acetate, 4-pentene-1-nitrile, 5-hexene-1-nitrile, 6-heptene-1-nitrile, 7-octene-1-nitrile, 8-nonene-1-nitrile, 9-decene-1-nitrile, 10-undecene-1-nitrile, 11-dodecene-1-nitrile, 12-tridecene-1-nitrile, 3-buten-1-ol trimethylsilyl ether, 4-penten-1-ol trimethylsilyl ether, 5-hexen-1-ol trimethylsilyl ether, 6-hepten-1-ol trimethylsilyl ether, 7-octen-1-ol trimethylsilyl ether, 8-nonen-1-ol trimethylsilyl ether, 9-decen-1-ol trimethylsilyl ether, 10-undecen-1-ol trimethylsilyl ether, 11-dodecen-1-ol trimethylsilyl ether, 12-tridecen-1-ol trimethylsilyl ether, 2,2-dimethyl-4-pentenal, undecylenic aldehyde, 2,4-dimethyl-2,6-heptadienal, 5-hexen-2-one, nonafluoro-1-hexene, 5-norbornene-2-carbonitrile, 5-norbornene-2-carboxaldehyde, 5-norbornene-2-carboxylic acid, cis-5-norbornene-endo-2,3-dicarboxylic acid, cis-5-norbornene-2-endo-3-exo-dicarboxylic acid, 5-norbornene-2-carboxylic acid methyl ester, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, cis-5-norbornene-exo-2,3-dicarboxylic anhydride, 5-norbornene-2-endo-3-endo-dimethanol, 5-norbornene-2-endo-3-exo-dimethanol, 5-norbornene-2-exo-3-exo-dimethanol, 5-norbornene-2,2,-dimethanol, 5-norbornene-2-methanol, 5-norbornen-2-ol, 5-norbornen-2-ol trimethylsilyl ether, 5-norbornen-2-ol methyl ether, 5-norbornen-2-yl acetate, 1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane, 2-benzoyl-5-norbornene, tricyclo[4.2.1.0^(0,0)]non-7-ene-3-carboxylic acid tert-butyl ester, tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxylic acid tert-butyl ester, tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxylic acid anhydride, N-butyl-tricyclo[4.2.1.0^(0,0)]non-7-ene-3,4-dicarboxyimide, 2-cyclopenten-1-one ethylene ketal, and vinylene carbonate.
 59. The copolymer of clam 51 wherein the olefin monomer is ethylene and the polar monomer is 7-octen-1-ol.
 60. The copolymer of clam 51 wherein the olefin monomer is ethylene and the polar monomer is 7-octen-1-ol trimethylsilyl ether.
 61. The copolymer of clam 51 wherein the olefin monomer is ethylene and the polar monomer is octenyl acetate.
 62. The copolymer of clam 51 wherein in which the olefin monomer is ethylene and the polar monomer is 5-norbornen-2-yl acetate.
 63. The copolymer of clam 51 wherein in which the olefin monomer is ethylene and the polar monomer is 5-norbornen-2-ol and or 5-norbornen-2-ol trimethylsilyl ether. 